CN110940709A - Method for improving sensitivity of gas sensor - Google Patents
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Abstract
The invention relates to a method for improving the sensitivity of a gas sensor, belonging to the field of gas sensors and the field of solid physics. The invention adopts manganese or magnesium metal as the electrode material which is contacted with the gas sensitive material, and utilizes the characteristic that the manganese or magnesium metal has lower work function compared with materials such as titanium, gold and the like, thereby realizing the effect of improving the sensitivity of the gas sensor only by changing the materials used for contacting the electrode. The invention provides a method for improving the sensitivity of a gas sensor, which can improve the sensitivity of the gas sensor by taking metal with larger difference value with the work function of a gas sensitive material as the metal for connecting the gas sensitive material. The method for improving the sensitivity is simple, and has no strong requirement on environmental conditions in the using process.
Description
Technical Field
The invention relates to a method for improving the sensitivity of a gas sensor, belonging to the field of gas sensors and the field of solid physics.
Background
A gas sensor is a sensor that detects the content of a certain gas or gases in the environment in which it is located. The gas sensor usually uses a gas sensitive material (gas sensitive) as a core for detection, and generates strong adsorption with one or more gas molecules in the air, so as to change the electrical properties of the material and finally obtain the information of the environmental gas by reading an electric signal.
However, the sensitivity of the novel gas sensor researched and reported in the last two decades is low at normal temperature, and a means for increasing the working temperature is mostly adopted in the method for obtaining high sensitivity, so that a lot of energy is consumed to provide a high-temperature environment, and high temperature is accompanied with many potential hazards, so that the application range and the application prospect of the gas sensor are greatly limited.
Disclosure of Invention
The invention aims to solve the problems of low sensitivity and poor effect at room temperature in the prior art, and provides a method for improving the sensitivity of a gas sensor; the method uses metal with larger difference value of work function with the gas sensitive material as an electrode to be connected with the gas sensitive material, thus achieving the purpose of improving the gas detection sensitivity.
The purpose of the invention is realized by the following technical scheme:
a method for improving the sensitivity of a gas sensor selects metal with larger work function difference with a gas sensitive material as an electrode contacted with the gas sensitive material; when the metal is contacted with the gas sensitive material, the larger the difference between the work functions of the metal and the gas sensitive material is, the more charges are accumulated on the interface of the metal and the gas sensitive material, when the device is exposed in a gas environment, the charges accumulated on the interface are transferred with gas molecules to form local electrons, and the local electrons generate an effect of influencing bias voltage by a built-in electric field, so that the sensitivity of the gas sensor is improved; the larger work function difference means that the absolute value of the difference is larger than 0.7 eV;
when the metal with larger difference of work functions of the gas sensitive material is contacted with the gas sensitive material, because of the low work function, a large amount of charges are accumulated at the contact interface of the metal and the gas sensitive material, when the device is exposed to the gas environment, the charges accumulated at the interface are subjected to charge transfer with gas molecules and are changed into local electrons, and the local charges generate an additional built-in electric field (V)p) The effect of the bias voltage is changed, thereby improving the sensitivity of the gas sensor. The larger the difference between the work functions of the metal and the gas sensitive material is, the more charges are accumulated at the contact interface, which results in the larger the built-in electric field formed by the adsorbed gas molecules, and further results in the higher sensitivity of the gas sensor. Therefore, the metal with larger difference value of work function with the gas sensitive material is very suitable for being used as the gas sensitive material in the gas sensorThe metals in contact with the alloy include Pt (5.65eV), Mn (4.1eV), and Mg (3.66 eV).
The high-sensitivity gas sensor prepared by the method comprises the following steps: the gas sensor comprises a gas sensitive material, an insulating substrate, a conductive electrode (the constituent material of the conductive electrode is metal with larger work function difference with the gas sensitive material) and a lead; the gas sensitive material is arranged on the insulating substrate, and the conductive electrode is arranged on the gas sensitive material and the insulating substrate and exists as an electrode in direct contact with the gas sensitive material; and a lead is connected on the manganese or magnesium metal electrode, so that the whole sensor is conveniently connected into an electronic system.
A protective layer is added on the surface of the electrode; the surface does not include a surface in contact with the gas sensitive material; the protective layer is made of a stable material;
the protective layer can be formed by means of covering, film plating, electroplating, partial oxidation and the like, so that the manganese or magnesium material is protected from being damaged by deterioration changes such as oxidation corrosion of the external environment and the like.
The stable material is a material which can exist in the air for a long time and is not easy to deteriorate, such as metal gold, plastic, silicon dioxide and the like.
The gas sensitive material includes: two-dimensional materials, semiconductors;
the two-dimensional material (referring to a material in the nanoscale range in thickness) includes: SnS2、SnS、SnSe2、SnSe、GaSe、GeSe、WS2、WSe2、MoS2、MoSe2、VS2、VSe2、PtS2、PtSe2And graphene, and the like;
the semiconductor includes: tin dioxide, zinc oxide, titanium dioxide, silver oxide, tungsten oxide, iron oxide and the like, and various doped materials based on the tin dioxide, the zinc oxide, the titanium dioxide, the silver oxide, the tungsten oxide, the iron oxide and the like.
The above list of gas sensitive materials is not all gas sensitive materials, and it is understood that it is the intention of this application that all gas sensitive materials improve gas sensor performance by contacting with metal to form as large a work function difference as possible.
The insulating substrate is used for bearing the gas sensitive material and has insulating property, so that electrons cannot be communicated with the two metal electrodes through the substrate.
The metal electrode is formed by any method, such as but not limited to, forming a metal electrode part to cover and connect with the gas sensitive material, and then a metal layer is coated by a coating machine after a template is formed by a photoetching method.
The connecting wire refers to a part having a function of connecting the sensor to the electronic system, and the wire is not necessarily required as long as the sensor can be connected to the electronic system.
The electronic system is an electronic system which can detect gas response by using the gas sensor, apply bias voltage and read and analyze feedback signals.
Advantageous effects
1. The invention provides a method for improving the sensitivity of a gas sensor, which can improve the sensitivity of the gas sensor by taking metal with larger difference value with the work function of a gas sensitive material as the metal for connecting the gas sensitive material. The method has the advantages that the method for improving the sensitivity is simple, and no strong requirement is placed on environmental conditions in the using process, for example, some sensors which need high-temperature environment to have good sensitivity need to be heated, and the heating consumes energy and is accompanied with danger hidden danger.
2. The invention provides a method for improving the sensitivity of a gas sensor, which has the effect of improving the sensitivity and has universality. The gas sensor with insufficient sensitivity at room temperature is changed into a relatively good gas sensor with good sensitivity even at high temperature, and the sensitivity of the gas sensor is better by adopting the method.
Drawings
FIG. 1 is a schematic diagram of step 1 of transferring a sheet of gas-sensitive material onto an insulating substrate;
FIG. 2 is a schematic diagram of step 2, constructing a metal electrode on the side with the gas-sensitive material;
FIG. 3 is a schematic diagram of step 3, in which a conductive wire is attached to the electrode to facilitate connection to an electronic system;
FIG. 4 is a simplified three-dimensional view of a gas sensor with metal electrodes;
FIG. 5 is a simplified side view of a gas sensor with metal electrodes;
FIG. 6 is a schematic diagram of a gas sensor for detecting gas;
FIG. 7 is a comparative example of experimental tests for manganese and gold electrodes; in the diagram (A), the contact electrode material is manganese metal, and the gas-sensitive material is SnS2At different concentrations of NO2Relative rate of change of resistance response in gas. In the diagram (B), the contact electrode material is gold metal, and the gas-sensitive material is SnS2At different concentrations of NO2Relative rate of change of resistance response in gas.
FIG. 8 is a schematic diagram of the effect of the built-in electric field at the metal-semiconductor contact interface on the gas sensor.
Detailed Description
In order to make the implementation objects, technical solutions and advantages of the present invention clearer, the following describes the scheme in the example of the present invention in more detail with reference to the accompanying drawings in the example of the present invention. In the drawings, the same or similar symbols denote the same or similar elements or elements having the same or similar functions. The described examples are examples of a portion, but not all, of the invention.
The examples described below with reference to the drawings are illustrative and intended to illustrate the invention and are not to be construed as limitations of the invention. All other embodiments based on the embodiments of the present invention can be obtained by those skilled in the art without any creative efforts, and the embodiments of the present invention are described in detail below with reference to the attached drawings.
In the description of the present invention, it is to be understood that the terms "upper", "lower", "large", "lower", "more", "lower", "reduction", "lower" and "larger" are used in an orientation, position or degree relationship based on the knowledge of the position, position or degree relationship as shown in the drawings, and are used for convenience in describing the invention and simplifying the description, but do not indicate or imply that the device or element referred to must have a particular orientation, be constructed in a particular orientation, and be operated, and therefore should not be construed as limiting the scope of the invention.
Example 1
A method for improving the sensitivity of gas sensor features that the metal of electrode connected to gas-sensitive material is replaced by Mn metal. The gas-sensitive material is SnS2；
As shown in FIG. 1, operation 1 transfers a sheet of gas sensitive material onto a sheet of insulating substrate, here exemplified as SnS2The material is transferred to a slide.
As shown in fig. 2, in operation 2, a mask is formed on the gas sensitive material, a suitable mask is formed by using an ultraviolet lithography method, then a manganese metal layer is plated on one side of the mask by using a vacuum evaporation method, and then the mask is cleaned by using acetone alcohol to form a required conductive electrode. For ease of illustration, only 2-terminal electrodes are shown, and more complex electrode structures may be used.
As shown in fig. 3, operation 3 is to wire the gas sensor into the electronic system to facilitate use of the device, to wire the gas sensor to a meter that can apply a specified bias voltage and read the current flowing through it.
As shown in fig. 4 and 5, the schematic diagram of the gas sensor of the manufactured manganese metal electrode is shown.
As shown in fig. 6, when the gas sensor is placed in an environment to be detected, molecules in the air can contact with the gas sensitive material, thereby affecting the electrical properties of the gas sensitive material and reacting gas components.
As shown in fig. 7, this is an experimental case given for ease of understanding. 2 gas sensors are respectively tested, and (A) manganese metal (4.1eV) is used as gas sensitive material SnS2(5.36eV) in contact with an electrode, the responsivity of which is reflected in a relative resistance change, with a maximum of 9ppm of NO213000% of signals are generated under the environment; in contrast, gold (5.1eV) is adopted as the gas-sensitive material SnS in the (B)2The response signal of the contacted electrode is only 15 percent.
Example 2
As shown in fig. 8, this is a schematic diagram showing the effect of the built-in electric field formed at the metal-semiconductor contact interface on the gas sensor.
The figure uses manganese metal (4.1eV) as electrode contact SnS2(5.36eV) gas sensitive Material, the absorbed target molecule is NO2。
In FIG. 8, the solid line shows adsorption of NO2The current-voltage relationship before the gas, the longitudinal dotted line being the bias voltage V applied across the sensor during detection0The horizontal dotted line is the current I corresponding at this moment0(ii) a When the sensor adsorbs NO2After gas molecules, part of charges accumulated on the metal semiconductor contact interface is bound, which is equivalent to reducing SnS at the interface2The metal semiconductor contact can reach the balance of the Fermi surface, electrons in the metal can continue to SnS2When the movement is detected, more charges are accumulated on one side of the semiconductor, and the extra charges are equivalent to form an extra built-in electric field VpIn FIG. 8, it corresponds to the intention to achieve a current value I equal to that before adsorption0Must be at the original bias voltage value V0Lower increase of Vp. Due to the bias voltage V in the detection0Is fixed and thus the current changes, i.e. the sensitivity increases.
Taking FIG. 6 as an example, a 3V bias is applied across the electrodes, wherein a 1V bias is divided between SnS2On the material body, the bias voltage of 2V is divided in SnS2At the interface in contact with the manganese metal. Conventional gas sensors primarily utilize SnS2Variations in the bulk of the material, while the present application discusses SnS2A change in contact interface with the metal. Therefore, to simplify the understanding of the role of a metal having a large difference in work function from a gas-sensitive material as a contact electrode, the current (I) before the sensor adsorbs gas moleculesbefor) And the current (I) after adsorption of gas moleculesafter) The expression of (c) is written as:
wherein A is the contact area of the electrode with the two-dimensional material, A* 2DIs the Richardson equivalent constant of a two-dimensional material, T is the absolute temperature value, e is the electron charge, kBIs the Boltzmann constant, VSBIs the Schottky barrier at the interface, η is the ideality factor, VpIs the built-in electric field formed at the interface. From the above formula, VpThe larger the difference between the current before and after adsorption of the gas molecules, the higher the sensitivity.
The application is to protect the electrode in contact with the gas sensitive material by using the metal with larger difference between the work function of the gas sensitive material and the work function of the electrode, namely because the work function of manganese (4.1eV) or magnesium (3.66eV) is lower than that of other metals, or the work function of platinum (5.65eV) is higher than that of other metals (considering that the metal with practical application significance at normal temperature, such as potassium metal, has no practical application significance when spontaneously combusted in air, although the work function is lower than 2.3 eV), and V formed in the principle description is based on the principlepAnd the sensitivity is higher, so that the electrode is more suitable to be used as an electrode in contact with a gas sensitive material, and a high-sensitivity gas sensor is realized.
The above detailed description is intended to illustrate the objects, aspects and advantages of the present invention, and it should be understood that the above detailed description is only exemplary of the present invention and is not intended to limit the scope of the present invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (8)
1. A method of increasing the sensitivity of a gas sensor, comprising: selecting a metal with a larger work function difference with the gas sensitive material as an electrode in contact with the gas sensitive material; when the metal is contacted with the gas sensitive material, the larger the difference between the work functions of the metal and the gas sensitive material is, the more charges are accumulated on the interface of the metal and the gas sensitive material, when the device is exposed in a gas environment, the charges accumulated on the interface are transferred with gas molecules to form local electrons, and the local electrons generate an effect of influencing bias voltage by a built-in electric field, so that the sensitivity of the gas sensor is improved; the larger work function difference means that the absolute value of the difference is greater than 0.7 eV.
2. A method of increasing the sensitivity of a gas sensor as recited in claim 1, wherein: the metal includes: pt (5.65eV), Mn (4.1eV), and Mg (3.66 eV).
3. A high sensitivity gas sensor prepared by the method of claim 1 or 2, wherein: the method comprises the following steps: the gas sensor comprises a gas sensitive material, an insulating substrate, a conductive electrode and a lead; the gas sensitive material is arranged on the insulating substrate, and the conductive electrode is arranged on the gas sensitive material and the insulating substrate and exists as an electrode in direct contact with the gas sensitive material; the Pt, manganese or magnesium metal electrode is connected with a lead, so that the whole sensor is conveniently connected into an electronic system.
4. A sensor as claimed in claim 3, wherein: a protective layer is added on the surface of the electrode; the surface does not include a surface in contact with the gas sensitive material; the protective layer is a stable material.
5. The method of claim 1, wherein: the gas sensitive material includes: two-dimensional materials and semiconductors.
6. The method of claim 5, wherein: the two-dimensional material is used for interacting parts with gas molecules in the environment, and comprises: SnS2、SnS、SnSe2、SnSe、GaSe、GeSe、WS2、WSe2、MoS2、MoSe2、VS2、VSe2、PtS2、PtSe2And graphene.
7. The method of claim 5, wherein: the semiconductor includes: tin dioxide, zinc oxide, titanium dioxide, silver oxide, tungsten oxide, iron oxide, and various doped materials based thereon.
8. The method of claim 1, wherein: the insulating substrate is used for bearing the gas sensitive material and has insulating property, so that electrons cannot be communicated with the two metal electrodes through the substrate;
the metal electrode is formed by any method, such as but not limited to, forming a metal electrode part to cover and connect with the gas sensitive material, and then plating a layer of metal by a film plating machine after forming a template by a photoetching method;
the connecting lead is a part with the function of connecting the sensor into the electronic system, and the lead is not required as long as the sensor can be connected into the electronic system;
the electronic system is an electronic system which can detect gas response by using the gas sensor, apply bias voltage and read and analyze feedback signals.
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Cited By (4)
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| CN113268866A (en) * | 2021-05-13 | 2021-08-17 | 国网山东省电力公司电力科学研究院 | Calculating C under the action of electric field5F10Method for adsorbing O insulating gas on copper surface |
| CN113466297A (en) * | 2021-08-23 | 2021-10-01 | 安徽砺剑防务科技有限公司 | Toxic gas detection sensing structure, sensor and application |
| CN114646419A (en) * | 2022-03-23 | 2022-06-21 | 中山大学 | Gas pressure sensor, preparation method thereof and gas pressure detection method |
| CN116253361A (en) * | 2023-03-09 | 2023-06-13 | 中国石油大学(华东) | WS (WS) 2 /SnSe 2 Nano heterogeneous material and nitrogen dioxide gas sensor as well as preparation methods and applications thereof |
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| CN116253361A (en) * | 2023-03-09 | 2023-06-13 | 中国石油大学(华东) | WS (WS) 2 /SnSe 2 Nano heterogeneous material and nitrogen dioxide gas sensor as well as preparation methods and applications thereof |
| CN116253361B (en) * | 2023-03-09 | 2024-05-03 | 中国石油大学(华东) | WS (WS)2/SnSe2Nano heterogeneous material and nitrogen dioxide gas sensor as well as preparation methods and applications thereof |
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Application publication date: 20200331 |