CN112881475B - Porous SiCO-MoO3 high-temperature hydrogen sensor and preparation method thereof - Google Patents
Porous SiCO-MoO3 high-temperature hydrogen sensor and preparation method thereof Download PDFInfo
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- CN112881475B CN112881475B CN202110023551.XA CN202110023551A CN112881475B CN 112881475 B CN112881475 B CN 112881475B CN 202110023551 A CN202110023551 A CN 202110023551A CN 112881475 B CN112881475 B CN 112881475B
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- 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
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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
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Abstract
The invention discloses a porous SiCO-MoO 3 The high-temperature hydrogen sensor comprises a magnetron sputtering silicon substrate, wherein a composite gas-sensitive film layer is arranged on the upper surface of the magnetron sputtering silicon substrate, and an electrode layer is arranged on the upper surface of the composite gas-sensitive film layer; the composite gas-sensitive film layer comprises a MoO3 layer, a carbon nanotube layer and a porous SiCO layer which are sequentially arranged from top to bottom, the porous SiCO layer is arranged on the upper surface of the magnetron sputtering silicon substrate, a SiBCO intermediate layer is arranged between the porous SiCO layer and the magnetron sputtering silicon substrate, and the MoO layer is arranged on the upper surface of the magnetron sputtering silicon substrate 3 Al is arranged between the layers and the electrode layer 2 O 3 An intermediate layer. The invention has excellent hydrogen sensitive characteristic and high temperature stability, and the preparation cost is low.
Description
Technical Field
The invention relates to the field of hydrogen sensors, in particular to porous SiCO-MoO 3 A high-temperature hydrogen sensor and a preparation method thereof.
Background
Hydrogen energy is inexhaustible clean energy, is the element with the highest calorific value in fossil energy except nuclear energy, and has wide development prospect in the fields of new energy automobiles, fuel cells, home heating, aerospace and the like. However, hydrogen is flammable and explosive gas, the problem of hydrogen induction must be solved to realize the application of hydrogen energy, and it is of great significance to develop a high-sensitivity hydrogen sensor to detect low-concentration hydrogen in the environment and monitor hydrogen leakage. The atmosphere detection is not only required to be rapid and accurate, but also the detection system is required to be small in size and light in weight, and the traditional atmosphere detection mode cannot be sufficient. With the rapid development of scientific technology, gas sensors with good performance under high temperature conditions are urgently needed in more and more fields such as aerospace, aviation, military, oil exploration, nuclear energy, communication and the like.
Because the forbidden band width of silicon is small, the silicon device is difficult to operate at a high temperature higher than 250 ℃, and especially when high working temperature, high power, high frequency and strong radiation environmental conditions coexist, the silicon device cannot be sufficient. The motor vehicle having a catalytic converter is based primarily on TiO2 or ZrO2Metal oxide sensors, but the sensitive object is the oxygen content in the gas. The silicon carbide gas sensor can detect hydrogen-containing compounds such as H2, cxHy and the like and can work at a high temperature of more than 400 ℃, but the long-term stability and the reliability of the silicon carbide gas sensor are poor. In addition, most of the existing hydrogen sensors need catalytic alloy to decompose and chemically adsorb hydrogen molecules, so that the main problems of high preparation cost, harmful substances and the like are caused. Molybdenum trioxide (MoO) 3 ) Has the characteristics of high electrochemical activity, low thermal stability, high specific surface area and the like, and MoO is generated at high temperature 3 Has specific sensing capability to hydrogen, but MoO 3 The sensitivity of the hydrogen sensor is yet to be further optimized. In summary, the gas sensitivity, mechanical reliability and economy are key problems to be solved urgently for the high-temperature hydrogen sensor.
Disclosure of Invention
The invention aims to provide porous SiCO-MoO 3 A high-temperature hydrogen sensor and a preparation method thereof. The invention has excellent hydrogen sensitive characteristic and high temperature stability, and the preparation cost is low.
The technical scheme of the invention is as follows: porous SiCO-MoO 3 The high-temperature hydrogen sensor comprises a magnetron sputtering silicon substrate, wherein a composite gas-sensitive film layer is arranged on the upper surface of the magnetron sputtering silicon substrate, and an electrode layer is arranged on the upper surface of the composite gas-sensitive film layer; the composite gas-sensitive film layer comprises MoO arranged from top to bottom in sequence 3 The composite material comprises a layer, a carbon nanotube layer and a porous SiCO layer, wherein the porous SiCO layer is arranged on the upper surface of a magnetron sputtering silicon substrate, a SiBCO intermediate layer is arranged between the porous SiCO layer and the magnetron sputtering silicon substrate, and the MoO layer is arranged on the upper surface of the magnetron sputtering silicon substrate 3 Al is arranged between the layers and the electrode layer 2 O 3 An intermediate layer.
The porous SiCO-MoO 3 In a high temperature hydrogen sensor, the MoO 3 The thickness of the layer is 280-320nm, the thickness of the carbon nanotube layer is 180-220nm, the thickness of the porous SiCO layer is 280-320nm, the thickness of the SiBCO intermediate layer is 80-120nm, and the Al is 2 O 3 The thickness of the intermediate layer is 80-120nm.
The aforementioned porous SiCO-MoO 3 In a high temperature hydrogen sensor, the MoO 3 The thickness of the layer is 300nm, the thickness of the carbon nanotube layer is 200nm, the thickness of the porous SiCO layer is 300nm, the thickness of the SiBCO middle layer is 100nm, and Al 2 O 3 The thickness of the intermediate layer was 100nm.
The aforementioned porous SiCO-MoO 3 The preparation method of the high-temperature hydrogen sensor comprises the following steps,
step 1: cleaning a magnetron sputtering silicon substrate, and performing vacuum drying on the cleaned magnetron sputtering silicon substrate;
step 2: carrying out ion beam sputtering cleaning on the surface of the magnetron sputtering silicon substrate under the high vacuum condition;
and 3, step 3: forming a SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate subjected to ion beam sputtering cleaning through magnetron sputtering, taking the magnetron sputtering silicon substrate with the SiBCO intermediate layer formed on the surface as a substrate, and performing ion beam sputtering cleaning on the surface of the substrate;
and 4, step 4: then a porous SiCO layer, a carbon nanotube layer and MoO are sequentially formed on the surface of the substrate in a magnetron sputtering mode 3 Layer and Al 2 O 3 An intermediate layer.
The aforementioned porous SiCO-MoO 3 In the preparation method of the high-temperature hydrogen sensor, the SiBCO interlayer is formed by the steps of taking Si, graphite and boron as targets, introducing argon with the purity of 99.99% as working gas and oxygen with the purity of 99.99% as reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.1: and 0.9, controlling the flow of argon to be 25sccm, performing magnetron sputtering for 60min, and thus forming the SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate.
The aforementioned porous SiCO-MoO 3 In the preparation method of the high-temperature hydrogen sensor, the method for forming the porous SiCO layer comprises the steps of taking Si and graphite as target materials, introducing argon with the purity of 99.99% as working gas and oxygen with the purity of 99.99% as reaction gas under the conditions that the sputtering pressure is 0.3Pa and the substrate temperature is 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.3:0.7, controlling the flow of argon to be 25sccm, carrying out magnetron sputtering, andthe magnetron sputtering time is 90min, so that a SiCO layer is formed on the surface of the SiBCO intermediate layer, the substrate with the SiCO layer formed on the surface is immersed in a hydrofluoric acid solution with the concentration of 50% for 6 min, then immersed in a low-concentration hydrofluoric acid solution with the concentration of 20% for 60min to obtain a porous SiCO layer, the residual hydrofluoric acid on the surface of the obtained dust bottom with the porous SiCO layer is cleaned by using distilled water, and finally the porous SiCO layer is dried in a drying box at the temperature of 120 ℃ for 40 min to remove residual moisture.
The aforementioned porous SiCO-MoO 3 In the preparation method of the high-temperature hydrogen sensor, the carbon nanotube layer is formed by using graphite as a target material, introducing argon with the purity of 99.99% as a working gas under the sputtering pressure of 0.2Pa and the substrate temperature of 200 ℃, controlling the flow of the argon to be 25sccm, performing magnetron sputtering for 60min, and thus forming the carbon nanotube layer on the surface of the porous SiCO layer.
The aforementioned porous SiCO-MoO 3 In the preparation method of the high-temperature hydrogen sensor, the MoO is formed 3 The method of the layer is that Mo is used as a target material, argon with the purity of 99.99 percent is introduced as a working gas and oxygen with the purity of 99.99 percent is introduced as a reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.4:0.6, controlling the flow of argon to be 25sccm, carrying out magnetron sputtering for 90min, and thus forming MoO on the surface of the carbon nanotube layer 3 And (3) a layer.
The aforementioned porous SiCO-MoO 3 In the preparation method of the high-temperature hydrogen sensor, the Al is formed 2 O 3 The layer is formed by Al 2 O 3 Introducing argon with the purity of 99.99 percent as working gas as a target material under the sputtering pressure of 0.2Pa and the substrate temperature of 200 ℃, controlling the flow of the argon to be 25sccm, carrying out magnetron sputtering for 60min, and thus obtaining the target material in MoO 3 Al is formed on the surface of the layer 2 O 33 And (3) a layer.
The aforementioned porous SiCO-MoO 3 In the preparation method of the high-temperature hydrogen sensor, the method for cleaning the magnetron sputtering silicon substrate comprises the steps of firstly ultrasonically cleaning the magnetron sputtering silicon substrate by acetone for 8 minutes and then respectively using deionized waterAnd (4) ultrasonically cleaning the silicon substrate by water and alcohol for 8 minutes, and repeating the above process for 4 times to complete the cleaning work of the magnetron sputtering silicon substrate.
Compared with the prior art, the invention has the following advantages:
1. the invention arranges a porous SiCO layer and MoO 3 Layer of SiCO and MoO 3 Has stronger gas-sensitive performance to hydrogen at high temperature of 500 ℃, and the main advantages of SiCO are high sensitivity, strong oxidation resistance and MoO 3 Has the main advantages of good specificity and quick response. Preparing a porous nanostructure layer on the SiCO layer, and further optimizing the hydrogen diffusion performance and the induction performance of the porous nanostructure layer; the invention is arranged on a porous SiCO layer and MoO 3 The carbon nanotube layer is arranged between the layers, so that the porous SiCO layer and the MoO layer are improved 3 Hydrogen interfacial diffusion properties and bond strength between layers. The gas-sensitive film system consisting of the SiCO layer, the MoO3 layer and the carbon nano tube layer has excellent gas-sensitive performance and high-temperature stability, films of all layers can be tightly combined in the induction process, the SiBCO intermediate layer is prepared between the porous SiCO layer and the magnetron sputtering silicon substrate, and the MoO intermediate layer is formed between the porous SiCO layer and the magnetron sputtering silicon substrate 3 Preparing Al between the layers and the electrode layer 2 O 3 The middle layer forms good expansion gradient, ensures that each layer of film can be tightly combined in the adsorption process, and enhances the adhesiveness between the substrate, the gas-sensitive film system and the electrode.
2. The invention relates to porous SiCO-MoO through a specific preparation method 3 Preparing a high-temperature hydrogen sensor, mainly cleaning a magnetron sputtering silicon substrate, and performing vacuum drying on the cleaned magnetron sputtering silicon substrate; carrying out ion beam sputtering cleaning on the surface of the magnetron sputtering silicon substrate under the high vacuum condition, wherein the first action is to remove impurity particles on the surface of the substrate; the ion bombardment can activate atoms on the surface of the substrate, and enhance the adhesion strength of the film to the substrate; forming a SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate subjected to ion beam sputtering cleaning through magnetron sputtering, taking the magnetron sputtering silicon substrate with the SiBCO intermediate layer formed on the surface as a substrate, and performing ion beam sputtering cleaning on the surface of the substrate; then a porous SiCO layer, a carbon nanotube layer and MoO are sequentially formed on the surface of the substrate in a magnetron sputtering mode 3 Layer and Al 2 O 3 An intermediate layer.
Drawings
FIG. 1 is a schematic structural view of the present invention;
FIG. 2 is a graph of the dynamic response of the present invention to hydrogen at 500 ℃;
FIG. 3 shows the present invention for hydrogen, CO, acetone and H at different temperatures 2 O induction response diagram.
1. Magnetron sputtering a silicon substrate; 2. compounding a gas-sensitive film layer; 3. a porous SiCO layer; 4. a carbon nanotube layer; 5. MoO 3 A layer; 6. al (Al) 2 O 3 An intermediate layer; 7. an electrode layer; 8. and a SiBCO interlayer.
Detailed Description
The invention is further illustrated by the following figures and examples, which are not to be construed as limiting the invention.
Example (b): porous SiCO-MoO 3 As shown in fig. 1, the high-temperature hydrogen sensor comprises a magnetron sputtering silicon substrate 1, wherein a composite gas-sensitive thin film layer is arranged on the upper surface of the magnetron sputtering silicon substrate 1, and an electrode layer 7 is arranged on the upper surface of the composite gas-sensitive thin film layer 2; the composite gas-sensitive film layer 2 comprises MoO arranged from top to bottom in sequence 3 Layer 5, carbon nanotube layer 4 and porous SiCO layer 3, porous SiCO layer 3 sets up the upper surface at magnetron sputtering silicon substrate 1, and is equipped with SiBCO intermediate level 2 between porous SiCO layer 3 and magnetron sputtering silicon substrate 1, moO 3 Al is provided between the layer 5 and the electrode layer 7 2 O 3 An intermediate layer 6.
The MoO 3 The thickness of the layer 5 is 280-320nm, the thickness of the carbon nanotube layer 4 is 180-220nm, the thickness of the porous SiCO layer 3 is 280-320nm, the thickness of the SiBCO intermediate layer 8 is 80-120nm, and the Al is added 2 O 3 The thickness of the intermediate layer 6 is 80-120nm.
The MoO 3 The thickness of the layer 5 is 300nm, the thickness of the carbon nanotube layer 4 is 200nm, the thickness of the porous SiCO layer 3 is 300nm, the thickness of the SiBCO8 middle layer is 100nm, and the Al is 2 O 3 The thickness of the intermediate layer 6 was 100nm.
The invention is provided with a plurality of holesSiCO layer 3 and MoO 3 Layer 5, because of SiCO and MoO 3 The gas-sensitive performance to hydrogen at high temperature of 500 ℃ is strong, the main advantages of SiCO are high sensitivity and strong oxidation resistance, and the main advantages of MoO3 are good specificity and quick response. Preparing a porous nanostructure layer on the SiCO layer, and further optimizing the hydrogen diffusion performance and the induction performance of the porous nanostructure layer; the invention is arranged on a porous SiCO layer 3 and MoO 3 A carbon nanotube layer 4 is arranged between the layers 5, so that the porous SiCO layer 3 and the MoO are improved 3 Hydrogen interfacial diffusion properties and bond strength between layers 5. From a SiCO layer, moO 3 The gas-sensitive film system composed of the layer 5 and the carbon nanotube layer 4 has excellent gas-sensitive performance and high-temperature stability, each layer of film can be tightly combined in the induction process, a SiBCO intermediate layer 8 is prepared between the porous SiCO layer 3 and the magnetron sputtering silicon substrate 1, and the MoO is subjected to the reaction 3 Al is prepared between layer 5 and electrode layer 7 2 O 3 The middle layer 6 forms a good expansion gradient, ensures that each layer of film can be tightly combined in the adsorption process, and enhances the adhesiveness between the substrate, the gas-sensitive film system and the electrode.
The porous SiCO-MoO 3 The preparation method of the high-temperature hydrogen sensor is characterized by comprising the following steps: comprises the following steps of (a) carrying out,
step 1: cleaning a magnetron sputtering silicon substrate, and performing vacuum drying on the cleaned magnetron sputtering silicon substrate; the method for cleaning the magnetron sputtering silicon substrate comprises the steps of ultrasonically cleaning the magnetron sputtering silicon substrate by using acetone for 8 minutes, then ultrasonically cleaning the substrate by using deionized water and alcohol for 8 minutes respectively, and repeating the cleaning process for 4 times to complete the cleaning work of the magnetron sputtering silicon substrate.
Step 2: carrying out ion beam sputtering cleaning on the surface of the magnetron sputtering silicon substrate under the high vacuum condition;
and step 3: forming a SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate subjected to ion beam sputtering cleaning through magnetron sputtering, taking the magnetron sputtering silicon substrate with the SiBCO intermediate layer formed on the surface as a substrate, and performing ion beam sputtering cleaning on the surface of the substrate; the method for forming the SiBCO intermediate layer comprises the steps of taking Si, graphite and boron as targets, introducing argon with the purity of 99.99% as working gas and oxygen with the purity of 99.99% as reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.1: and 0.9, controlling the flow of argon to be 25sccm, performing magnetron sputtering for 60min, and thus forming the SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate.
And 4, step 4: then a porous SiCO layer, a carbon nanotube layer and MoO are sequentially formed on the surface of the substrate in a magnetron sputtering mode 3 Layer and Al 2 O 3 An intermediate layer.
The method for forming the porous SiCO layer comprises the steps of taking Si and graphite as targets, introducing argon with the purity of 99.99% as working gas and oxygen with the purity of 99.99% as reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.3: and 0.7, controlling the flow of argon to be 25sccm, carrying out magnetron sputtering for 90min, so as to form a SiCO layer on the surface of the SiBCO intermediate layer, immersing the substrate with the SiCO layer formed on the surface into a hydrofluoric acid solution with the concentration of 50% for 6 min, then immersing the substrate into a low-concentration hydrofluoric acid solution with the concentration of 20% for 60min, so as to obtain a porous SiCO layer, cleaning the residual hydrofluoric acid on the surface of the obtained dust bottom with the porous SiCO layer by using distilled water, and finally drying the substrate in a drying oven at 120 ℃ for 40 min to remove residual moisture.
The method for forming the carbon nanotube layer comprises the steps of introducing argon with the purity of 99.99% as working gas under the sputtering pressure of 0.2Pa and the substrate temperature of 200 ℃ by taking graphite as a target material, controlling the flow of the argon to be 25sccm, carrying out magnetron sputtering for 60min, and forming the carbon nanotube layer on the surface of the porous SiCO layer.
Said MoO formation 3 The method of the layer is that Mo is used as a target material, argon with the purity of 99.99 percent is introduced as a working gas and oxygen with the purity of 99.99 percent is introduced as a reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.4:0.6, controlling the flow of argon to be 25sccm, carrying out magnetron sputtering for 90min, and thus forming MoO on the surface of the carbon nanotube layer 3 And (3) a layer.
The above-mentionedForm Al of 2 O 3 The layer is formed by Al 2 O 3 Introducing argon with the purity of 99.99 percent as working gas as a target material under the sputtering pressure of 0.2Pa and the substrate temperature of 200 ℃, controlling the flow of the argon to be 25sccm, carrying out magnetron sputtering for 60min, and thus obtaining the target material in MoO 3 Al is formed on the surface of the layer 2 O 33 And (3) a layer.
For the porous SiCO-MoO 3 And (3) testing the high-temperature hydrogen sensor, cutting the composite gas-sensitive film layer sample into small blocks of 8mm multiplied by 8mm, manufacturing an electrode on the surface of the film sample by using silver paste, and leading out a fine copper wire from the electrode. The silicon chip welded on the tube seat is packaged by a 100-mesh double-layer stainless steel net and a clamping ring to form the sensor, and then the sensor is placed in an aging table to be electrified and aged so as to increase the stability of the sensor. The test system mainly comprises main parts of gas supply, heating constant temperature, I-V characteristic test, automatic control and the like. The two gases are respectively controlled by the digital gas mass flow controllers 1 and 2, so that mixed gas or the two gases alternately enter the reaction cavity to participate in reaction. In order to test the high-temperature characteristics of the sensor, two electrodes are led out from the conductive screw by using a high-temperature resistant aviation lead and connected to a semiconductor parameter analyzer, so that the response characteristics of the sensor under different conditions can be measured. Wherein FIG. 2 is a dynamic response curve of a porous SiCO-MoO3 sensor to hydrogen at a temperature of 500 ℃. As can be seen, the sensor has high sensitivity to hydrogen gas and has a fast response time under high temperature conditions.
The porous SiCO-MoO 3 The inductive response coefficients of the high-temperature hydrogen sensor to hydrogen, CO, acetone and H2O at different temperatures are shown in FIG. 3, wherein the inductive response coefficients are expressed by the formula
It is found that Gf and G0 are the steady state conductivities measured in the target gas and air environments, respectively. As can be seen from FIG. 3, porous SiCO-MoO was observed at temperatures ranging from 400 ℃ to 600 ℃ 3 The sensor has high sensitivity to hydrogen and CO and H 2 O and acetone hardly induce and show excellent selectivity。
The working principle is as follows: by providing a porous SiCO layer 3 and MoO 3 Layer 5, because of SiCO and MoO 3 Has stronger gas-sensitive performance to hydrogen at high temperature of 500 ℃, and the main advantages of SiCO are high sensitivity, strong oxidation resistance and MoO 3 Has the main advantages of good specificity and quick response. Preparing a porous nanostructure layer on the SiCO layer, and further optimizing the hydrogen diffusion performance and the induction performance of the porous nanostructure layer; the invention is arranged on a porous SiCO layer 3 and MoO 3 A carbon nanotube layer 4 is arranged between the layers 5, so that the porous SiCO layer 3 and the MoO are improved 3 Hydrogen interfacial diffusion properties and bond strength between layers 5. From a SiCO layer, moO 3 The gas-sensitive film system composed of the layer 5 and the carbon nanotube layer 4 has excellent gas-sensitive performance and high-temperature stability, each layer of film can be tightly combined in the induction process, a SiBCO intermediate layer 8 is prepared between the porous SiCO layer 3 and the magnetron sputtering silicon substrate 1, and the MoO is subjected to the reaction 3 Al is prepared between layer 5 and electrode layer 7 2 O 3 And the interlayer 6 forms a good expansion gradient, ensures that each layer of film can be tightly combined in the adsorption process, and enhances the adhesiveness between the substrate, the gas-sensitive film system and the electrode.
Claims (6)
1. Porous SiCO-MoO 3 High temperature hydrogen sensor, its characterized in that: the composite gas-sensitive sputtering device comprises a magnetron sputtering silicon substrate (1), wherein a composite gas-sensitive film layer is arranged on the upper surface of the magnetron sputtering silicon substrate (1), and an electrode layer (7) is arranged on the upper surface of a composite gas-sensitive film layer (2); the composite gas-sensitive film layer (2) comprises MoO (MoO) which is sequentially arranged from top to bottom 3 Layer (5), carbon nanotube layer (4) and porous SiCO layer (3), porous SiCO layer (3) set up the upper surface at magnetron sputtering silicon substrate (1), and are equipped with SiBCO intermediate level (2) between porous SiCO layer (3) and magnetron sputtering silicon substrate (1), moO 3 Al is arranged between the layer (5) and the electrode layer (7) 2 O 3 An intermediate layer (6); the MoO 3 The thickness of the layer (5) is 280-320nm, the thickness of the carbon nanotube layer (4) is 180-220nm, the thickness of the porous SiCO layer (3) is 280-320nm, the thickness of the SiBCO intermediate layer (8) is 80-120nm, and the Al is doped with the silicon-based oxygen and the silicon-based oxygen, and is formed by the following steps of 2 O 3 The thickness of the intermediate layer (6) is 80-120nm;
the preparation method of the porous SiCO-MoO3 high-temperature hydrogen sensor comprises the following steps,
step 1: cleaning a magnetron sputtering silicon substrate, and performing vacuum drying on the cleaned magnetron sputtering silicon substrate;
step 2: carrying out ion beam sputtering cleaning on the surface of the magnetron sputtering silicon substrate under the high vacuum condition;
and step 3: forming a SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate subjected to ion beam sputtering cleaning through magnetron sputtering, taking the magnetron sputtering silicon substrate with the SiBCO intermediate layer formed on the surface as a substrate, and performing ion beam sputtering cleaning on the surface of the substrate; the method for forming the SiBCO intermediate layer comprises the steps of taking Si, graphite and boron as targets, introducing argon with the purity of 99.99% as working gas and oxygen with the purity of 99.99% as reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.1:0.9, controlling the flow of argon to be 25sccm, performing magnetron sputtering for 60min, and thus forming a SiBCO intermediate layer on the surface of the magnetron sputtering silicon substrate;
and 4, step 4: then sequentially forming a porous SiCO layer, a carbon nanotube layer, a MoO3 layer and an Al2O3 intermediate layer on the surface of the substrate in a magnetron sputtering mode; the method for forming the porous SiCO layer comprises the steps of taking Si and graphite as targets, introducing argon with the purity of 99.99% as working gas and oxygen with the purity of 99.99% as reaction gas under the conditions that the sputtering pressure is 0.3Pa and the substrate temperature is 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.3: and 0.7, controlling the flow of argon to be 25sccm, carrying out magnetron sputtering for 90min, so as to form a SiCO layer on the surface of the SiBCO intermediate layer, immersing the substrate with the SiCO layer formed on the surface into a hydrofluoric acid solution with the concentration of 50% for 6 min, then immersing the substrate into a low-concentration hydrofluoric acid solution with the concentration of 20% for 60min, so as to obtain a porous SiCO layer, cleaning the residual hydrofluoric acid on the surface of the obtained dust bottom with the porous SiCO layer by using distilled water, and finally drying the substrate in a drying oven at 120 ℃ for 40 min to remove residual moisture.
2. The porous SiCO-MoO3 high temperature hydrogen sensor of claim 1, wherein: the thickness of the MoO3 layer (5) is 300nm, the thickness of the carbon nanotube layer (4) is 200nm, the thickness of the porous SiCO layer (3) is 300nm, the thickness of the SiBCO (8) middle layer is 100nm, and the thickness of the Al2O3 middle layer (6) is 100nm.
3. The porous SiCO-MoO of claim 1 3 High temperature hydrogen sensor, its characterized in that: the method for forming the carbon nanotube layer comprises the steps of introducing argon with the purity of 99.99% as working gas under the sputtering pressure of 0.2Pa and the substrate temperature of 200 ℃ by taking graphite as a target material, controlling the flow of the argon to be 25sccm, carrying out magnetron sputtering for 60min, and forming the carbon nanotube layer on the surface of the porous SiCO layer.
4. The porous SiCO-MoO3 high temperature hydrogen sensor of claim 1, wherein: the method for forming the MoO3 layer comprises the steps of taking Mo as a target material, introducing argon with the purity of 99.99% as a working gas and oxygen with the purity of 99.99% as a reaction gas under the sputtering pressure of 0.3Pa and the substrate temperature of 200 ℃, wherein the ratio of the introduced argon to the introduced oxygen is 0.4: and 0.6, controlling the flow of argon to be 25sccm, performing magnetron sputtering for 90min, and thus forming a MoO3 layer on the surface of the carbon nanotube layer.
5. The porous SiCO-MoO of claim 1 3 High temperature hydrogen sensor, its characterized in that: the method for forming the Al2O3 layer comprises the steps of introducing argon with the purity of 99.99% as working gas into Al2O3 serving as a target material under the sputtering pressure of 0.2Pa and the substrate temperature of 200 ℃, controlling the flow of the argon to be 25sccm, carrying out magnetron sputtering for 60min, and forming the Al2O33 layer on the surface of the MoO3 layer.
6. The porous SiCO-MoO of claim 1 3 High temperature hydrogen sensor, its characterized in that: the pairThe method for cleaning the magnetron sputtering silicon substrate comprises the steps of ultrasonically cleaning the magnetron sputtering silicon substrate by using acetone for 8 minutes, then ultrasonically cleaning the magnetron sputtering silicon substrate by using deionized water and alcohol for 8 minutes respectively, and repeating the cleaning process for 4 times to finish the cleaning work of the magnetron sputtering silicon substrate.
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| CN202110023551.XA CN112881475B (en) | 2021-01-08 | 2021-01-08 | Porous SiCO-MoO3 high-temperature hydrogen sensor and preparation method thereof |
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