CN112345480A - Method for integrating gas adsorption film and infrared surface plasma device for gas sensing and sensor - Google Patents
Method for integrating gas adsorption film and infrared surface plasma device for gas sensing and sensor Download PDFInfo
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
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- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4005—Concentrating samples by transferring a selected component through a membrane
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4005—Concentrating samples by transferring a selected component through a membrane
- G01N2001/4016—Concentrating samples by transferring a selected component through a membrane being a selective membrane, e.g. dialysis or osmosis
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Abstract
A method for integrating a gas adsorption film and an infrared surface plasma device for gas sensing and a sensor are provided, wherein a gas adsorption film and infrared surface plasma device integrated structure is arranged in a gas cavity of the gas sensor, the infrared surface plasma device comprises an artificial super surface structure and a substrate used as an infrared window and a support, and the gas adsorption film is manufactured on the artificial super surface structure; when gas enters the gas cavity and flows through the gas adsorption film and the infrared surface plasma device integrated structure, the gas is adsorbed and concentrated by the gas adsorption film, the infrared surface plasma device excites the surface plasma field to induce the change of the adsorption film, and the infrared detector detects the light absorption change information of infrared light passing through the infrared surface plasma device, so that the concentration information of the gas is obtained. The invention can overcome the defects that the traditional gas sensor has lower detection level and low sensitivity and can not detect the gas with ultra-low concentration.
Description
Technical Field
The invention relates to a gas detection technology, in particular to an optical gas infrared sensing technology.
Background
A gas sensor is a transducer that converts a certain gas volume fraction into a corresponding electrical signal.
The application of the gas sensor in the civil field is mainly embodied as follows: in the kitchen, the leakage of civil gas such as natural gas, liquefied petroleum gas, city gas and the like is detected, and the gas generated during the cooking of food in the microwave oven is detected, so that the microwave oven is automatically controlled to cook the food; the carbon dioxide sensor, the smoke sensor, the ozone sensor and the like are used in houses, buildings, meeting rooms and public entertainment places to control the automatic operation of the air purifier or the electric fan; in some high-rise buildings, the gas sensor may also be used to detect fire stutter and to alarm.
In the industrial field, gas sensors are mainly used in the petrochemical industry, and some carbon dioxide sensors, ammonia sensors, nitric oxide sensors and the like can be used in specific applications for detecting harmful gases such as carbon dioxide, ammonia gas, chlorine gas and the like. In addition, the method can be used for detecting organic solvents, phosphanes and other extremely toxic gases in the semiconductor and microelectronic industries; in the aspect of power industry, a hydrogen sensor can detect hydrogen generated in the deterioration process of power transformer oil; in the food industry, the gas sensor can also detect the freshness of perishable foods such as meat; in the fruit and vegetable preservation application, the gas sensor detects the concentration meters of oxygen, ethylene and carbon dioxide in the preservation warehouse so as to ensure the freshness and safety of fruits; the method has wide requirements in the aspects of detecting oxygen in waste gas in the automobile and kiln industry, detecting the concentration of ethanol gas in breath of drivers in road traffic and the like.
In the field of environmental monitoring most close to life, gas sensors are naturally not available. For example, a gas causing acid rain, such as nitrogen oxide, sulfur oxide, and hydrogen chloride, is detected by a sensor; carbon dioxide sensors, ozone sensors, freon, and the like detect greenhouse gases and the like. It is believed that the application range of the gas sensor will be wider and wider after further modification in the future, and the application of the gas sensor will be seen in more occasions.
At present, the gas sensing method includes an electrochemical method, a semiconductor metal oxide method, an infrared optical method, and the like. The optical gas infrared sensor has the advantages of high reliability, good selectivity, high precision, no toxicity, less interference from the environment, long service life and the like. The current detection method of infrared gas sensors is light source-gas chamber-infrared detector, such as patents CN110687065, CN110687064A, CN111208083A, CN210514064U, etc. The principle of the method is to measure the absorption rate of infrared gas to infrared light by utilizing Lambert beer law. However, in the case of a very dilute gas to be detected, the gas concentration is low, and this method cannot achieve reliable detection or cannot detect it at all. In this case, the infrared gas sensor has the disadvantages of low detection level, low sensitivity, and incapability of detecting gas with ultra-low concentration.
Disclosure of Invention
The invention provides a method for integrating a gas adsorption film and an infrared surface plasma device for gas sensing and a gas sensor, aiming at the defects in the prior art, the method is characterized in that the gas adsorption film is used for absorbing and concentrating thin gas, and then the infrared surface plasma device is used for exciting a surface plasma field to induce the change of the adsorption film so as to realize the detection of the gas, so that the defects that the traditional gas sensor is low in detection level, low in sensitivity and incapable of detecting the gas with ultralow concentration are overcome.
The technical scheme of the invention is as follows:
a method for integrating a gas adsorption film and an infrared surface plasma device for gas sensing is characterized in that a gas adsorption film and infrared surface plasma device integrated structure is arranged in a gas cavity of a gas sensor, the gas adsorption film and infrared surface plasma device integrated structure comprises the gas adsorption film and the infrared surface plasma device, the infrared surface plasma device comprises an artificial super surface structure and a substrate used as an infrared window and a support, and the gas adsorption film is manufactured on the artificial super surface structure. When infrared light irradiates the air cavity, gas is adsorbed and concentrated by the gas adsorption film when flowing through the infrared surface plasma device of the integrated gas adsorption film in the air cavity, the infrared surface plasma device excites the surface plasma field to induce the change of the adsorption film, and the infrared detector detects the light absorption change information of infrared light passing through the infrared surface plasma device, so that the concentration of the gas is obtained.
The invention further provides a gas sensor, and the gas sensor can realize the gas sensing method, and comprises a gas cavity, an infrared light source and an infrared detector which are arranged outside the gas cavity, wherein the gas cavity is provided with a gas inlet and a gas outlet. A gas adsorption film and infrared surface plasma device integrated structure is arranged in the gas cavity and between the light source and the detector; the integrated structure of the gas adsorption film and the infrared surface plasma device comprises the gas adsorption film and the infrared surface plasma device, the infrared surface plasma device comprises an artificial super surface structure and a substrate used as an infrared window and a support, and the gas adsorption film is manufactured on the artificial super surface structure.
Specifically, the infrared light source and the infrared detector are arranged at two ends of the outer side of the air cavity, and gas and light penetrate through the gas adsorption film and the infrared surface plasma device integrated structure from one end of the air cavity to the other end, and are of a transmission type structure.
Preferably, the artificial super-surface structure is composed of one or more super-surface arrays, and when a plurality of super-surface array groups are adopted, the array element structure of each super-surface array is different and respectively corresponds to one gas.
Preferably, the gas adsorption film is made of, but not limited to, a porous material represented by a metal organic framework Material (MOF), a high molecular polymer represented by Polyetherimide (PEI), polyisobutylene PIB, vinylpyridine P4V, and the like.
Preferably, the artificial super-surface structure is used for exciting a surface plasmon near field, and the material of the artificial super-surface structure can be a metal conductive material such as gold, silver, aluminum, platinum and the like.
Preferably, the substrate is used for supporting the artificial super-surface structure, and the material thereof may be, but is not limited to, a dielectric material such as calcium fluoride, magnesium fluoride, aluminum nitride, aluminum scandium nitride, silicon nitride, and the like.
An integrated gas adsorption film and infrared surface plasma device for gas sensing is provided, and the method
Compared with the traditional method for detecting the infrared absorption of the gas, the method provided by the invention is used for detecting the infrared absorption of the gas adsorption film. I.e. a membrane that converts direct detection of gas into detection of adsorbed and concentrated gas.
The gas adsorption film is used for absorbing and concentrating thin gas, and then the infrared surface plasma device is used for exciting the surface plasma field to induce the change of the adsorption film so as to realize the detection of the gas, so that the gas detection device can realize the rapid detection of the gas, has small volume, high sensitivity and high detection limit, and is suitable for the simultaneous detection of various gases. The method provides a high-sensitivity and high-performance gas detection method for industries such as industrial production, agricultural planting and daily life, thereby generating great benefits.
Drawings
FIG. 1 is a schematic diagram of a gas sensor;
FIG. 2 is a schematic view of a gas adsorption film and an infrared surface plasmon device integrated structure;
FIG. 3 is a schematic view of an artificial super-surface structure;
FIG. 4 is a schematic diagram of a super-surface array with cross-shaped array elements;
FIG. 5 is a schematic diagram of a combined structure of array elements of a super-surface array in a cross shape with different sizes;
FIG. 6 is a schematic diagram of a complex structure of array elements of a super-surface array.
FIG. 1. light source; 2. an air cavity; 3. a gas adsorption film; 4. an infrared surface plasmon device; 5. an infrared detector; 2-1. an air inlet; 2-2, air outlet, 4-1, artificial super surface structure; 4-2. infrared window substrate 6. super surface array.
Detailed Description
The present invention is described in further detail below with reference to the accompanying drawings.
The method for integrating the gas adsorption film and the infrared surface plasma device for gas sensing provided by the invention can be realized by the sensor structure shown in figure 1, and the gas sensor consists of three parts: 1. the device comprises a light source, a gas cavity and a detection module, wherein the detection module consists of a gas adsorption film 3, an infrared surface plasma device 4 and an infrared detector 5.
Usually, the infrared light source 1 and the infrared detector are arranged at two ends of the outer side of the air cavity, the air inlet and the air outlet are arranged on the air cavity, and the infrared light and the air flow enter from one end and exit from the other end. Infrared light is emitted from the light source 1 and is absorbed by the detection module after passing through the air cavity.
The unique place of the invention is that an infrared surface plasma device integrated structure of a gas adsorption film is arranged between an infrared light source 1 and an infrared detector 5. Namely, gas and light penetrate through the gas adsorption film from one end of the gas cavity to the other end of the gas cavity, and the gas cavity and the infrared surface plasma device are of a transmission type structure.
Referring to fig. 2, the infrared surface plasmon device integrated structure of the gas adsorption film comprises a gas adsorption film 3 and an infrared surface plasmon device 4, the infrared surface plasmon device comprises an artificial super surface structure 4-1 and a substrate 4-2 as an infrared window and support, and the gas adsorption film 4-2 can be fabricated on the artificial super surface structure 4-1 by spin coating or placing a chip in a solution. In the gas chamber 2, the gas adsorption film 3 faces the direction of gas flow, and the substrate 4-2 of the infrared surface plasmon device faces the direction of the detector. The gas adsorption film 3 functions to adsorb and concentrate gas. The artificial super-surface structure 4-1 has the function of exciting a surface plasma near field, and the substrate 4-1 is used for supporting the artificial super-surface structure.
The working process is as follows: infrared light is emitted from the light source 1 and absorbed by the air cavity backup detection module. The gas enters the gas cavity 2 through the gas inlet 2-1 and flows out of the gas outlet 2-2, the gas is adsorbed and concentrated by the gas adsorption film 3, the infrared surface plasma device 4 can excite an enhanced electric field to induce the change of the gas adsorption film 3, and the infrared detector 5 detects the light absorption change condition of infrared light passing through the infrared surface plasma device 4.
The working principle is as follows: the gas causes the absorption change of the gas adsorption film 3, and further causes the light absorption change of the infrared surface plasma device 4, and further is detected by the infrared detector 5. So that the concentration of the gas can be known from the change of the infrared detector 5.
According to the structure and the working mode, the sensor is small in size, can sense gas with high sensitivity and high speed, and particularly can sense multiple gases simultaneously.
In this example, as the material of the gas adsorption film 3, a porous material typified by a metal organic framework Material (MOF), a high molecular polymer typified by Polyetherimide (PEI), polyisobutylene PIB, vinylpyridine P4V, or the like can be used.
For the artificial super-surface structure 4-1, the material can be a metal conductive material such as gold, silver, aluminum, platinum and the like.
For the substrate 4-2, the material can be, but is not limited to, a dielectric material such as calcium fluoride, magnesium fluoride, aluminum nitride, scandium aluminum nitride, silicon nitride, etc.
As a preferred embodiment, referring to fig. 3, the artificial super-surface structure is composed of one or more super-surface arrays 6, and when a plurality of super-surface array sets are adopted, the array element structure of each super-surface array is different and corresponds to one gas respectively. For example, referring to fig. 4, the array elements of the super-surface array 6 of the artificial super-surface structure are cross-shaped, and fig. 5 is a cross-shaped combined structure with different sizes, and can also be composed of complex structures as shown in fig. 6.
These structures are merely exemplary, and one of ordinary skill in the art will recognize that other structures may perform the same function.
With the above technical solutions, the measurable gases include, but are not limited to, carbon oxide gases represented by carbon dioxide, nitrogen oxide gases represented by nitrogen dioxide, ozone, sulfur oxide gases represented by sulfur dioxide, sulfides represented by hydrogen sulfide, combustible gases represented by methane, greenhouse gases, and the like.
While there has been shown and described what are at present considered to be the fundamental principles and essential features of the invention and its advantages, it will be understood by those skilled in the art that the invention is not limited by the foregoing embodiments, but is capable of numerous changes without departing from the spirit and scope of the invention, such insubstantial changes being made within the scope of the invention as claimed.
Claims (8)
1. A method for integrating a gas adsorption film and an infrared surface plasma device for gas sensing is characterized in that a gas adsorption film and infrared surface plasma device integrated structure is arranged in a gas cavity of a gas sensor, the gas adsorption film and infrared surface plasma device integrated structure comprises a gas adsorption film and an infrared surface plasma device, the infrared surface plasma device comprises an artificial super surface structure and a substrate used as an infrared window and a support, and the gas adsorption film is manufactured on the artificial super surface structure; when gas enters the gas cavity and flows through the gas adsorption film and the infrared surface plasma device integrated structure, the gas is adsorbed and concentrated by the gas adsorption film, the infrared surface plasma device excites the surface plasma field to induce the change of the adsorption film, and the infrared detector detects the light absorption change information of infrared light passing through the infrared surface plasma device, so that the concentration information of the gas is obtained.
2. A gas sensor, realize the method of claim 1, it includes air cavity and infrared light source and infrared detector that is mounted outside the air cavity, there are air inlets and air outlets on the air cavity; the infrared surface plasma device integrated structure is characterized in that a gas adsorption film and infrared surface plasma device integrated structure is arranged in the gas cavity and between the light source and the detector; the integrated structure of the gas adsorption film and the infrared surface plasma device comprises the gas adsorption film and the infrared surface plasma device, the infrared surface plasma device comprises an artificial super surface structure and a substrate used as an infrared window and a support, and the gas adsorption film is manufactured on the artificial super surface structure.
3. The gas sensor according to claim 2, wherein the infrared light source and the infrared detector are disposed at both ends of the outside of the gas chamber, and the gas and light are transmitted from one end of the gas chamber to the other end through the gas adsorption film and the infrared surface plasmon device integrated structure, and are of a transmissive structure.
4. The gas sensor according to claim 2 or 3, wherein the gas adsorption film of the integrated structure of the gas adsorption film and the infrared surface plasmon device faces the direction of gas flow, and the substrate of the infrared surface plasmon device faces the detector.
5. A gas sensor according to claim 2 or 3, wherein the artificial super-surface structure is composed of one or more super-surface arrays, and when a plurality of super-surface arrays are adopted, the array element structure of each super-surface array is different and corresponds to one gas.
6. The gas sensor according to claim 2 or 3, wherein the gas adsorption film is a porous material represented by, but not limited to, Metal Organic Framework (MOF), a high molecular polymer represented by Polyetherimide (PEI), polyisobutylene PIB, vinylpyridine P4V, or the like.
7. The gas sensor according to claim 2 or 3, wherein the artificial super-surface structure is used for exciting the surface plasmon near-field, and the material thereof can be a metal conductive material such as gold, silver, aluminum, platinum and the like.
8. The gas sensor according to claim 2 or 3, wherein the substrate is used for supporting an artificial super-surface structure and is made of a dielectric material, such as but not limited to calcium fluoride, magnesium fluoride, aluminum nitride, aluminum scandium nitride, silicon nitride, etc.
Priority Applications (1)
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