CN106124575B - NO (nitric oxide)2Sensor and preparation method thereof - Google Patents
NO (nitric oxide)2Sensor and preparation method thereof Download PDFInfo
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- CN106124575B CN106124575B CN201610641966.2A CN201610641966A CN106124575B CN 106124575 B CN106124575 B CN 106124575B CN 201610641966 A CN201610641966 A CN 201610641966A CN 106124575 B CN106124575 B CN 106124575B
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- 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
Abstract
The invention discloses a NO2A sensor and a method for manufacturing the same. The sensor comprises an oxide single crystal substrate, WO3Epitaxial thin film, test electrode and noble metal catalyst, by WO between test electrodes3NO in epitaxial film resistance value change calibration environment2The gas concentration. The technical scheme of the invention is to regulate and control the oxide single crystal substrate and WO3Stress at epitaxial film interface to realize WO3Epitaxial thin film structural element' WO6Distortion and tilting of octahedron' to obtain WO with specific crystal phase and exposed crystal face, high surface activity and reaction site concentration and stable performance3Epitaxial thin film and increasing NO thereby2The detectability and stability of the sensor. The sensor provided by the invention can detect the concentration of 40 mu g/m3To 20mg/m3 NO2Short response time and stable performance, and can be used for NO in atmospheric environment2The real-time monitoring of the concentration has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of metal oxide based resistance type gas sensing, and particularly relates to a gas sensor based on WO3NO of epitaxial thin film2A sensor and a method for manufacturing the same.
Background
With the rapid development of economy, nitrogen dioxide (NO) emitted from automobiles and factories2) Has become one of the main atmospheric pollutants, seriously threatening human health. The world health organization research shows that the people with lower immunity are in NO2The concentration is 20 to 200 μ g/m3When the patient lives in the environment for 1-8 hours, symptoms such as pulmonary hypofunction, airway inflammation and the like can appear. When NO is present2The concentration is 41.7mg/m3Even short term exposure can be life threatening. Thus, both China and WHO convert NO2The 1-hour concentration limit and the annual average concentration limit of (2) are set to 200. mu.g/m3And 40. mu.g/m3。
NO commonly used at present2The detection techniques include spectrophotometry, chemiluminescence, and differential absorption spectroscopy. These methods can accurately measure NO2Concentration, but expensive detection instrument and complicated operation flow are required, and NO is difficult to realize2And (5) monitoring the concentration in real time. Resistive NO using metal oxide as sensitive material2The sensor has the advantages of small volume, low cost, full solid state and the like, and is expected to replace the existing detection method to realize NO detection2The multi-point online detection has wide market prospect.
Among the numerous metal oxides, WO3For NO2Having excellent selectivity is the hot spot of current research. In the published literature, WO3Radical NO2The sensor usually employs WO3Nanomaterials, e.g. mesoporous WO3Powder and hollow WO3Nanospheres and WO3A nanowire. These nanomaterials are typically monoclinic phase WO that are stable at room temperature and have low surface energy3Therefore, response times are generally longer (>120 s). And the nano material is easy to agglomerate in the manufacturing and using processes of the sensor, so that the performance of the sensor is unstable, such as sensitivity reduction, baseline resistance drift and the like. Meanwhile, WO3The preparation process of the nano material is complex, and the popularization of the nano material is hindered due to low mass production repeatability.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the WO-based sensor which has short response time, high sensitivity, stable performance and batch production3NO of epitaxial thin film2A sensor and a method for manufacturing the same.
The technical scheme for realizing the purpose of the invention is to provide NO2The preparation method of the sensor comprises the following steps:
(1) placing the cleaned oxide single crystal substrate in a vacuum coating device, and growing WO at the rate of 0.01-10 nm per second at the temperature of 400-800 DEG C3Film to obtain tetragonal phase WO3An epitaxial thin film;
(2) first of all, in WO3Epitaxial thin film surface preparationTest electrodes, again in WO3Depositing a noble metal catalyst on the surface of the epitaxial film; or in the first place in WO3Depositing noble metal catalyst on the surface of the epitaxial film, and then depositing the noble metal catalyst on the surface of the epitaxial film3Preparing a test electrode on the surface of the epitaxial film; to obtain a NO2A sensor.
The vacuum coating device is one of laser molecular beam epitaxy, sputtering, evaporation or chemical vapor deposition devices; in a laser molecular beam epitaxy device, a KrF pulse laser with the frequency of 1Hz and the power of 350mW is used for bombarding WO3And (4) the surface of the solid target.
In WO3And depositing a noble metal catalyst on the surface of the epitaxial film by adopting a vacuum evaporation or sputtering method.
The oxide single crystal substrate is chemically changed into one of the following oxides: al (Al)2O3、SrTiO3、LaAlO3、MgO。
The noble metal catalyst is one of Ag, Au, Pd, Pt, Cu and Ni.
The noble metal catalyst is one of simple substance Ag, Au, Pd, Pt, Cu and Ni compounds.
The technical scheme of the invention also comprises NO obtained by the preparation method2A sensor.
NO provided by the invention2Sensor made of oxide single crystal substrate, WO3The device comprises an epitaxial film, a test electrode and a noble metal catalyst; by measuring WO between test electrodes in different gas environments3NO in epitaxial film resistance value change calibration environment2The gas concentration; using oxide single crystal substrates and WO3WO regulation and control by stress at epitaxial film interface3Epitaxial thin film structural element' WO6Distortion and tilting of octahedron' to obtain WO with specific crystal phase and exposed crystal face, high surface activity and reaction site concentration and stable performance3Epitaxial thin film and increasing NO thereby2The detectability and stability of the sensor.
The invention is based on the principle that: WO3The epitaxial film has a single, stable and manually controllable crystal phase and an exposed crystal face,is ideal NO2The material is probed. The invention uses the oxide single crystal substrate and WO from the perspective of crystal structure regulation3Stress control of epitaxial thin film interface WO3Film structural element' WO6Distortion and tilting of octahedron "to make tetragonal or orthorhombic metastable phase WO existed at high temperature3Can exist stably at room temperature. These high temperature phases WO3The exposed crystal face has higher surface activity and is beneficial to improving NO2And (4) detecting efficiency. At the same time, WO3The lattice mismatch between the epitaxial thin film and the oxide single crystal substrate is described in WO3More oxygen vacancy and other reaction sites are introduced to the surface of the epitaxial film to promote NO2Adsorption and reaction and further improve the performance of the sensor.
Compared with the prior art, the invention has the advantages that:
1. using oxide single crystal substrates and WO3The crystal structure of the epitaxial film interface stress control film is obtained, and the WO with higher surface activity and reaction site concentration is obtained3Epitaxial thin film and increasing NO thereby2The detection efficiency of the sensor.
2、WO3The epitaxial film has stable crystal structure, chemical composition and surface appearance, and can effectively improve NO2Stability of the sensor.
3、WO3The epitaxial film is prepared by laser molecular beam epitaxy or other vacuum coating methods, has the advantages of good process repeatability, compatibility with micromachining technology and the like, and can realize batch production.
Drawings
FIG. 1 shows WO provided in an embodiment of the present invention3Epitaxial thin film NO2The structure of the sensor is shown schematically, wherein 1, an oxide single crystal substrate; 2. WO3An epitaxial thin film; 3. a test electrode; 4; noble metal catalyst particles.
FIG. 2 shows SrTiO provided by an embodiment of the invention3(001) Epitaxial growth of WO on single crystal substrate3X-ray diffraction spectra of the films.
FIG. 3 shows SrTiO provided by an embodiment of the invention3(001) Single crystal substrate and W grown thereonO3Reflective high energy electron diffraction patterns of epitaxial thin films.
FIG. 4 is a diagram of WO provided in an embodiment of the present invention3The concentration of the epitaxial film sensor pair is 40 mu g/m3To 20mg/m3Time NO2The test results of (1).
Detailed Description
The technical scheme of the invention is further explained by combining the drawings and the specific embodiment.
Example 1
Referring to FIG. 1, there is provided NO in the present example2Schematic structure of sensor using SrTiO3(001) For the single crystal substrate, the sensor adopts Laser molecular beam epitaxy (Laser-MBE) method to grow WO on the oxide single crystal substrate 13Epitaxial film 2, preparation of test electrodes 3, and application of the same to WO3Depositing noble metal catalyst particles 4 on the surface of the epitaxial film to produce NO2A sensor. The specific manufacturing process is as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 600 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
Referring to FIG. 2, this example provides SrTiO3(001) On and off a single crystal substrateGrowth extension of WO3X-ray diffraction (XRD) spectrum of the film in a scanning pattern of theta-2 theta (wherein:. sup.3Diffraction peaks of single crystal substrate.
Referring to FIG. 3, it is SrTiO in this example3(001) Single crystal substrate and WO grown thereon3Reflective High Energy Electron Diffraction (RHEED) pattern of the epitaxial film. With SrTiO3(001) The similar XRD diffraction peaks and striped RHEED diffraction fringes of the single crystal substrate indicate that the WO grown in the embodiment3The film is an epitaxial film having good crystal quality. WO was measured by XRD and RHEED3The lattice parameter of the film, it is shown that the tetragonal phase WO is obtained under the growth conditions of this example3And (3) epitaxial thin films.
See FIG. 4, which is a diagram of the tetragonal phase WO provided in this example at a test temperature of 200 deg.C3The epitaxial film pair concentration was 40. mu.g/m3To 20mg/m3 NO2Resistance response curve of (1). The test result shows that the concentration of the sensor pair is only 40 mu g/m3NO of2Still has strong resistance response and can realize trace NO2And (6) detecting. Meanwhile, the concentration of the sensor pair is 20mg/m3 NO2Has a response time of only 20s, and can realize high concentration NO2The rapid detection of the method effectively guarantees personal safety. The sensor has stable resistance baseline and can stably work in a long-term test of nearly 1 year. The sensor can therefore be used for NO in an atmospheric environment2And (5) monitoring the concentration in real time.
Example 2
The materials and process steps adopted in the embodiment are basically the same as those of the embodiment 1, and only WO in the step (2)3The growth rate of the epitaxial thin film was adjusted to 10 nm/s.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 3
NO provided in this example2The sensor comprises the following preparation steps:
（1）cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 600 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
(4) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 4
The manufacturing steps of the embodiment are as follows:
(1) and cleaning the MgO (001) single crystal substrate. Putting the MgO (001) single crystal substrate into an acetone solution for ultrasonic cleaning for 5 minutes, taking out the MgO (001) single crystal substrate, washing the MgO (001) single crystal substrate with deionized water, putting the MgO (001) single crystal substrate into an HF solution for corrosion for 5 minutes, and then washing and drying the MgO (001) single crystal substrate with the deionized water to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. The MgO (001) single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 600 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3Material is instantaneously evaporated and deposited on the surface of MgO (001) single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3Surface evaporation of epitaxial thin filmsAnd depositing an Au electrode.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 5
LaAlO is adopted in the embodiment3(001) The single crystal substrate, other materials, and process conditions were the same as in example 1.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 6
This example uses Al2O3（01 2) The single crystal substrate, other materials, and process conditions were the same as in example 1.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 7
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was put into an ion beam sputtering coating apparatus and heated to 600 ℃ to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3Epitaxial thin filmAnd Au electrodes are evaporated and deposited on the surface.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 8
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 300 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film is a polycrystalline film rather than an epitaxial film because the substrate temperature is too low to achieve epitaxial growth.
Example 9
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) Putting the single crystal substrate into an acetone solution for ultrasonic cleaning for 5 minutes, taking out the single crystal substrate, washing the single crystal substrate with deionized water, putting the single crystal substrate into an HF solution for corrosion for 5 minutes, and then putting the single crystal substrate into the acetone solution for ultrasonic cleaningThen rinsing with deionized water and drying to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 400 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is resistant to NO2The test results of (2) are comparable to those of example 1.
Example 10
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 800 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film is an epitaxial film with good crystalline quality, which is NO2The test results of (2) are comparable to those of example 1.
Example 11
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 900 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By sputter deposition in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film is a polycrystalline film rather than an epitaxial film, since the substrate temperature is too high to cause WO3The film epitaxial orientation is disordered.
Example 12
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 600 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By evaporation in WO3Making Pt particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film being an epitaxial film, to NO2The test results of (2) are comparable to those of example 1.
Example 13
The manufacturing steps of the embodiment are as follows:
(1) cleaning SrTiO3(001) A single crystal substrate. Mixing SrTiO3(001) The single crystal substrate is placed into an acetone solution for ultrasonic cleaning for 5 minutes, is taken out, is washed by deionized water and is placed into an HF solution for corrosion for 5 minutes, and then is washed by deionized water and is dried to obtain a clean single crystal substrate.
(2) Growth of WO3And (3) epitaxial thin films. Mixing SrTiO3(001) The single crystal substrate was placed in a laser molecular beam epitaxy apparatus and heated to 600 ℃. Bombarding WO with KrF pulse laser of 1Hz and 350mW3Surface of solid target material, to which WO is added3The material is instantaneously evaporated and deposited to SrTiO3(001) Surface of a single crystal substrate to obtain WO3The growth rate of the epitaxial film is about 0.01 nm/s.
(3) Using a stainless steel mask in WO3And evaporating and depositing an Au electrode on the surface of the epitaxial film.
(4) By sputtering in WO3Making Ni particles on the surface of the epitaxial film as NO2The detected catalyst.
XRD and RHEED test results show that the deposited WO3The film being an epitaxial film, to NO2The test result of (2) is weaker than that of example 1, which is caused by the fact that Ni has a weaker catalytic performance than Pt.
See table 1 for the main process parameters and product results for the sensors provided in examples 1-13 of the present invention.
TABLE 1
Example 3 differs from example 1 in that the order of step (3) and step (4) is interchanged.
Claims (6)
1. NO (nitric oxide)2The preparation method of the sensor is characterized by comprising the following steps:
(1) placing the cleaned oxide single crystal substrate in a vacuum coating device, and growing WO at the rate of 0.01-10 nm per second at the temperature of 400-800 DEG C3Film of WO3Material is instantaneously evaporated and deposited on the surface of the oxide single crystal substrate to obtain WO3Tetragonal epitaxial films and use of oxide single crystal substrates with WO3WO regulation and control by stress at epitaxial film interface3Epitaxial thin film structural element' WO6Distortion and tilting of octahedron' to obtain WO with specific crystal phase and exposed crystal face, high surface activity and reaction site concentration and stable performance3An epitaxial thin film; the vacuum coating device is a laser molecular beam epitaxy device; the chemical composition of the oxide single crystal substrate is one of the following oxides: al (Al)2O3、SrTiO3、LaAlO3、MgO；
(2) First of all, in WO3Preparing test electrode on the surface of epitaxial film, and then preparing test electrode on the surface of the epitaxial film in WO3Depositing a noble metal catalyst on the surface of the epitaxial film; or in the first place in WO3Depositing noble metal catalyst on the surface of the epitaxial film, and then depositing the noble metal catalyst on the surface of the epitaxial film3Preparing a test electrode on the surface of the epitaxial film; to obtain a NO2A sensor.
2. A NO according to claim 12The preparation method of the sensor is characterized by comprising the following steps: by vacuum evaporation or sputtering, in WO3And depositing a noble metal catalyst on the surface of the epitaxial film.
3. A NO according to claim 12The preparation method of the sensor is characterized by comprising the following steps: the noble metal catalyst is one of Ag, Au, Pd, Pt, Cu and Ni.
4. A NO according to claim 12The preparation method of the sensor is characterized by comprising the following steps: the noble metal catalyst is one of Ag, Au, Pd, Pt, Cu and Ni compounds.
5. A NO according to claim 12The preparation method of the sensor is characterized by comprising the following steps: in a laser molecular beam epitaxy device, a KrF pulse laser with the frequency of 1Hz and the power of 350mW is used for bombarding WO3And (4) the surface of the solid target.
6. An NO obtained by the process of claim 12A sensor.
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| NL2021056B1 (en) * | 2018-06-05 | 2019-12-11 | Univ Delft Tech | Hydrogen gas sensing with single-crystal WO3 ultra-thin films |
| CN109142467A (en) * | 2018-07-23 | 2019-01-04 | 杭州电子科技大学 | A kind of high sensitive NO2Gas sensor and preparation method thereof |
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