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CN114235903A - A gas sensor and method of making the same - Google Patents

A gas sensor and method of making the same Download PDF

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Publication number
CN114235903A
CN114235903A CN202010943336.7A CN202010943336A CN114235903A CN 114235903 A CN114235903 A CN 114235903A CN 202010943336 A CN202010943336 A CN 202010943336A CN 114235903 A CN114235903 A CN 114235903A
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substrate
gas
gas sensitive
gas sensor
sensitive part
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潘革波
陈子杨
张少辉
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • 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
    • G01N27/128—Microapparatus

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Abstract

本发明公开了一种气体传感器的制作方法，该制作方法包括：对基板进行部分氧化，使被氧化的部分成为气体敏感部；其中，基板由含有金属元素的半导体材料制成，气体敏感部与基板的未被氧化的部分之间形成异质结。本发明解决了现有的气体传感器的气敏层容易脱落的问题。

Figure 202010943336

The invention discloses a manufacturing method of a gas sensor. The manufacturing method includes: partially oxidizing a substrate, so that the oxidized part becomes a gas sensitive part; wherein, the substrate is made of a semiconductor material containing metal elements, and the gas sensitive part is A heterojunction is formed between the unoxidized portions of the substrate. The invention solves the problem that the gas sensitive layer of the existing gas sensor is easy to fall off.

Figure 202010943336

Description

Gas sensor and manufacturing method thereof
Technical Field
The invention relates to the technical field of gas sensors, in particular to a gas sensor with a gas-sensitive layer integrally formed with a substrate and a manufacturing method thereof.
Background
A gas sensor is a transducer that converts a certain gas volume fraction into a corresponding electrical signal, and can be used in a variety of life situations, such as: detecting the formaldehyde concentration in a newly decorated room, or detecting the alcohol concentration of a drunk driver, and the like.
Existing gas sensors are generally fabricated by coating a gas-sensitive material layer on a ceramic substrate. However, the current manufacturing process cannot ensure that the gas sensitive material can be uniformly coated on the ceramic substrate. Therefore, the gas sensor manufactured by the above manufacturing method is not suitable for use in a severe environment because the bonding force between the gas sensitive layer and the ceramic substrate is not uniform, and the gas sensitive layer is likely to fall off. Moreover, the detachment of the gas sensitive layer affects the gas sensitivity of the gas sensor.
Disclosure of Invention
In view of the defects in the prior art, the invention provides the following technical scheme:
according to an aspect of the present invention, there is provided a method of manufacturing a gas sensor, the method comprising:
partially oxidizing the substrate to make the oxidized part become a gas sensitive part; wherein the substrate is made of a semiconductor material containing a metal element, and a heterojunction is formed between the gas sensitive part and a part of the substrate that is not oxidized.
Preferably, before the oxidizing the portion, the manufacturing method further includes: and carrying out surface treatment on the part to be oxidized of the substrate to enable the surface of the part to be oxidized of the substrate to have a microstructure.
Preferably, after the oxidizing the portion, the manufacturing method further includes:
forming a first electrode on the gas sensitive portion;
forming a second electrode on the gas sensitive portion or on the substrate outside the gas sensitive portion.
Preferably, after the first electrode and the second electrode are formed, the manufacturing method further includes: a heating unit is disposed on the substrate outside the gas sensitive portion.
Preferably, the method of forming the heating unit comprises:
forming an adhesive layer on the substrate except the gas sensitive portion;
the heating unit is arranged on the pasting layer.
According to an aspect of the present invention, there is provided a gas sensor including a substrate and a gas sensitive portion formed by partially oxidizing the substrate; wherein the substrate is made of a semiconductor material containing a metal element, and a heterojunction is formed between the gas sensitive part and a part of the substrate that is not oxidized.
Preferably, a microstructure is formed on a surface of the gas sensitive portion.
Preferably, the gas sensor further comprises a first electrode and a second electrode, the first electrode is disposed on the gas sensitive portion, and the second electrode is disposed on the gas sensitive portion or the substrate outside the gas sensitive portion.
Preferably, the gas sensor further comprises a heating unit disposed on the substrate outside the gas sensitive portion.
Preferably, the gas sensor further includes an adhesive layer formed on the substrate outside the gas sensitive portion, and the heating unit is disposed on the substrate through the adhesive layer.
The substrate and the gas sensitive part of the gas sensor manufactured by the manufacturing method provided by the invention are of an integrated structure, so that no bonding force exists between the substrate and the gas sensitive part, and the gas sensor is used even in a severe environment. Further, since the gas sensitive portion of the gas sensor of the present invention is formed by oxidizing a portion of the substrate, the gas sensitive portion is less likely to disappear, thereby ensuring stable gas sensitivity of the gas sensor.
Drawings
FIG. 1 is a flow chart of a method of fabricating a gas sensor according to an embodiment of the invention;
FIG. 2a is a schematic diagram of a gas sensor according to an embodiment of the invention;
fig. 2b is a schematic structural diagram of a gas sensor according to another embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, embodiments of the present invention are described in detail below with reference to the accompanying drawings. Examples of these preferred embodiments are illustrated in the accompanying drawings. The embodiments of the invention shown in the drawings and described in accordance with the drawings are exemplary only, and the invention is not limited to these embodiments. It should be noted that, in order to avoid obscuring the present invention with unnecessary details, only the structures and/or processing steps closely related to the scheme according to the present invention are shown in the drawings, and other details not so relevant to the present invention are omitted.
Further, it will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element or a surface of another element, the element may be directly on the other element or the surface of the other element, or intervening elements may also be present. Alternatively, when an element is referred to as being "directly on" another element or a surface of another element, there are no intervening elements present.
As described in the background art, existing gas sensors are generally fabricated by coating a gas sensitive material layer on a ceramic substrate. However, the gas sensor manufactured by the above manufacturing method is not suitable for use in a severe environment because the gas sensitive layer is easily peeled off.
In view of the above-mentioned problems of the prior art, an embodiment of the present invention provides a method for manufacturing a gas sensor, so as to integrally form a substrate and a gas sensitive portion, thereby solving the problem that a gas sensitive layer of the conventional gas sensor is easy to fall off.
A method of manufacturing a gas sensor according to an embodiment of the present invention will be described in detail below with reference to the accompanying drawings.
Example 1
The embodiment provides a manufacturing method of a gas sensor, as shown in fig. 1, the manufacturing method includes:
step S1, a substrate 1 made of a semiconductor material containing a metal element is provided. Preferably, the substrate 1 is made of AlGaInN material.
Step S2 is to partially oxidize the substrate 1 so that the oxidized portion becomes the gas sensitive portion 11. Specifically, the method of oxidizing the portion of the substrate 1 may employ a strong oxidant reaction process or an ultraviolet light assisted oxidation process. The specific range of the portion may be determined according to actual situations, for example: the portion may occupy the entire area of one side of the substrate 1 as shown in fig. 2a, or the portion may occupy a partial area of one side of the substrate 1 as shown in fig. 2 b.
The substrate 1 and the gas sensitive part 11 of the gas sensor manufactured by the manufacturing method provided by the embodiment are of an integral structure, so that no bonding force exists between the substrate 1 and the gas sensitive part 11, and the gas sensor is used even in a severe environment. Since the gas sensitive part 11 of the present embodiment is actually the oxidized portion of the substrate 1, the gas sensitive part 11 is also not easily disappeared, thereby ensuring stable gas sensitivity of the gas sensor.
In addition, the substrate 1 of the present embodiment is made of AlGaInN material, so that the mechanical properties and chemical stability of the gas sensor can be improved.
In the present embodiment, the specific material forming the substrate 1 may be replaced by one of AlGaN, AlN, GaN, GaInN and AlInN.
Further, the method for manufacturing the gas sensor of the present embodiment further includes a step of forming the first electrode 21 and the second electrode 22. Wherein the first electrode 21 and the second electrode 22 are both formed on the gas sensitive portion 11; alternatively, the first electrode 21 is formed on the gas sensitive portion 11, and the second electrode 22 is formed on the substrate 1 outside the gas sensitive portion 11. When the second electrode 22 is formed on the substrate 1 outside the gas sensitive part 11, a heterojunction is formed between the gas sensitive part 11 and the substrate 1, which is advantageous in improving the sensitivity of the gas sensor.
The working principle of the gas sensor of the embodiment is as follows:
in a general air environment, oxygen molecules in the air are adsorbed on the surface of the gas sensitive part of the gas sensor, and the oxygen molecules deprive electrons in a conduction band of the gas sensitive part and are converted into oxygen anions (O)-). A depletion layer may be formed in the heterojunction of the gas sensor during this process, resulting in an increase in the resistance of the gas sensor. When hydrogen sulfide (H) is present2S) and the likeThe hydrogen sulfide gas reacts with the oxygen anions and releases electrons into a depletion layer of a heterojunction of the gas sensor, so that the resistance of the gas sensor can be reduced, the increase of the conductivity of the gas sensor is improved, a current signal is changed, and the hydrogen sulfide gas can be detected. This change in current signal becomes more pronounced as the concentration of hydrogen sulfide gas or oxygen anions increases.
Example 2
Unlike embodiment 1, in the manufacturing method of this embodiment, before oxidizing the portion, the manufacturing method further includes: and performing surface treatment on the portion to be oxidized of the substrate 1 to make the surface of the portion to be oxidized of the substrate have a microstructure. The specific form of the microstructure can be determined according to actual needs. Preferably, the microstructures may be columnar structures or blind hole structures arranged in an array.
In this embodiment, after the above steps, the gas sensitive portion 11 formed by subsequent oxidation has the above microstructure, and the microstructure can increase the surface area of the gas sensitive portion 11, thereby increasing the contact area between the gas sensitive portion 11 and the detection gas, and thus improving the sensitivity of the gas sensor.
Example 3
Unlike embodiment 1, the manufacturing method of the present embodiment further includes a step of disposing a heating unit 3 on the substrate 1 except for the gas sensitive portion 11 after forming the first electrode 21 and the second electrode 22.
Specifically, an adhesive layer 4 is formed on the substrate 1 except for the gas sensitive part 11, and the heating unit 3 is provided on the adhesive layer 4 after the adhesive layer 4 is formed. The heating unit 3 is used for adjusting the temperature of the substrate 1 and the gas sensitive part 11, so that the temperature of the gas sensitive part 11 is close to the temperature of the surrounding gas to be detected, thereby further improving the detection sensitivity of the gas sensor.
Example 4
The present embodiment provides a gas sensor manufactured by the manufacturing method provided in the above-mentioned embodiments, and as shown in fig. 2a or fig. 2b, the gas sensor includes a substrate 1, a gas sensitive portion 11, a first electrode 21, and a second electrode 22. The gas sensitive portion 11 is formed by oxidizing a portion of the substrate 1. Wherein the substrate 1 is made of a semiconductor material containing a metal element. The first electrode 21 is disposed on the gas sensitive portion 11, and the second electrode 22 is disposed on the gas sensitive portion 11 or the substrate 1 outside the gas sensitive portion 11.
Preferably, the semiconductor material containing a metal element is one of AlGaInN, AlGaN, AlN, GaN, GaInN, AlInN.
Preferably, a microstructure is formed on the surface of the gas sensitive portion 11 to increase the contact area between the gas sensitive portion 11 and the detection gas.
Further, the gas sensor further comprises a heating unit 3, and the heating unit 3 is arranged on the substrate 1 outside the gas sensitive part 11. Specifically, an adhesive layer 4 is formed on the substrate 1 except for the gas sensitive part 11, and the heating unit 3 is disposed on the substrate 1 through the adhesive layer 4.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (10)

1.一种气体传感器的制作方法，其特征在于，所述制作方法包括：1. a preparation method of a gas sensor, is characterized in that, described preparation method comprises: 对基板进行部分氧化，使被氧化的所述部分成为气体敏感部；其中，所述基板由含有金属元素的半导体材料制成，所述气体敏感部与所述基板的未被氧化的部分之间形成异质结。Partially oxidize the substrate, so that the oxidized part becomes a gas sensitive part; wherein, the substrate is made of a semiconductor material containing a metal element, and the gap between the gas sensitive part and the unoxidized part of the substrate form a heterojunction. 2.根据权利要求1所述的制作方法，其特征在于，对所述部分进行氧化之前，所述制作方法还包括：对所述基板的将被氧化的部分进行表面处理，使所述基板的将被氧化的部分的表面具有微结构。2 . The manufacturing method according to claim 1 , wherein, before oxidizing the part, the manufacturing method further comprises: performing a surface treatment on the part of the substrate to be oxidized, so as to make the part of the substrate to be oxidized. The surface of the part to be oxidized has a microstructure. 3.根据权利要求1或2所述的制作方法，其特征在于，对所述部分进行氧化后，所述制作方法还包括：3. The manufacturing method according to claim 1 or 2, characterized in that, after the part is oxidized, the manufacturing method further comprises: 在所述气体敏感部上形成第一电极；forming a first electrode on the gas sensitive part; 在所述气体敏感部或者在所述气体敏感部之外的所述基板上形成第二电极。A second electrode is formed on the gas sensitive part or on the substrate other than the gas sensitive part. 4.根据权利要求3所述的制作方法，其特征在于，形成所述第一电极和所述第二电极之后，所述制作方法还包括：在所述气体敏感部之外的所述基板上设置加热单元。4 . The manufacturing method according to claim 3 , wherein after forming the first electrode and the second electrode, the manufacturing method further comprises: on the substrate other than the gas sensitive part. 5 . Set up the heating unit. 5.根据权利要求4所述的制作方法，其特征在于，形成所述加热单元的方法包括：5. The manufacturing method according to claim 4, wherein the method for forming the heating unit comprises: 在所述气体敏感部之外的所述基板上形成粘贴层；forming an adhesive layer on the substrate other than the gas sensitive part; 在所述粘贴层上设置所述加热单元。The heating unit is provided on the adhesive layer. 6.一种气体传感器，其特征在于，包括基板和气体敏感部，所述气体敏感部通过对所述基板进行部分氧化而形成；其中，所述基板由含有金属元素的半导体材料制成，气体敏感部与所述基板的未被氧化的部分之间形成异质结。6. A gas sensor, characterized by comprising a substrate and a gas sensitive part, the gas sensitive part being formed by partially oxidizing the substrate; wherein the substrate is made of a semiconductor material containing a metal element, and the gas A heterojunction is formed between the sensitive portion and the unoxidized portion of the substrate. 7.根据权利要求6所述的气体传感器，其特征在于，所述气体敏感部的表面上形成有微结构。7 . The gas sensor according to claim 6 , wherein microstructures are formed on the surface of the gas sensing portion. 8 . 8.根据权利要求6或7所述的气体传感器，其特征在于，所述气体传感器还包括第一电极和第二电极，所述第一电极设置于所述气体敏感部上，所述第二电极设置于所述气体敏感部或者所述气体敏感部之外的所述基板上。8. The gas sensor according to claim 6 or 7, wherein the gas sensor further comprises a first electrode and a second electrode, the first electrode is provided on the gas sensitive part, and the second electrode is provided on the gas sensitive part. The electrodes are arranged on the gas sensitive part or the substrate other than the gas sensitive part. 9.根据权利要求8所述的气体传感器，其特征在于，所述气体传感器还包括加热单元，所述加热单元设置于所述气体敏感部之外的所述基板上。9 . The gas sensor according to claim 8 , wherein the gas sensor further comprises a heating unit, and the heating unit is provided on the substrate outside the gas sensitive part. 10 . 10.根据权利要求9所述的气体传感器，其特征在于，所述气体传感器还包括粘贴层，所述粘贴层形成在所述气体敏感部之外的所述基板上，所述加热单元通过所述粘贴层设置于所述基板上。10 . The gas sensor according to claim 9 , wherein the gas sensor further comprises an adhesive layer, the adhesive layer is formed on the substrate other than the gas sensitive part, and the heating unit passes through the heating unit. 11 . The adhesive layer is disposed on the substrate.
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