CN114791449B - Gas sensor and preparation method and application thereof - Google Patents
Gas sensor and preparation method and application thereof Download PDFInfo
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Abstract
The invention relates to a gas sensor, a preparation method and application thereof, and relates to the technical field of gas sensors. The gas sensor comprises a matrix, wherein the surface of the matrix is also provided with GeTeO x A film and an elemental co-doped CuO film; the GeTeO is x The middle part of the film and the element co-doped CuO film are overlapped and form a heterostructure, the GeTeO x The film and the part of the CuO film co-doped with the element extend to the substrate, the GeTeO x The end parts of the film and the CuO film co-doped with the elements are provided with conductive metal films, wherein x is more than 0 and less than or equal to 4. The gas sensor pair H of the invention 2 S、NH 3 、NO 2 Has high sensitivity and lower detection limit. The higher the test temperature, the lower the detection limit and the higher the sensitivity. The invention has simple operation and simple reaction condition, and the magnetron sputtering method has low price and uniform film formation, can be used for preparing the vessel sensor components on a large scale, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to a gas sensor and a preparation method and application thereof.
Background
The gas sensor is a component for detecting the composition and content of gas. A gas sensor is generally considered to be a transducer that converts a certain gas volume fraction into a corresponding electrical signal.
With the development of technology, people pay attention to environmental safety problems gradually, and the problems of air pollution and the like are also paid more attention to. In order to ensure personal safety and prevent accidents, the air quality of various places in life is monitored in real time, and the concentration of toxic and harmful dangerous gases is very necessary to detect. Currently, monitoring and detection of various gases has been widely applied to various fields of medical and health, mine safety, pollution source investigation, environmental monitoring, industrial production, and the like. For example, alcohol gas of drunk driving, formaldehyde gas emitted from interior materials, nitrogen oxides in automobile exhaust emission, methane in petroleum coal mine, ammonia gas, hydrogen sulfide gas and the like are involved in traffic safety. It would clearly be highly competitive in the marketplace if one sensor could be designed to simultaneously detect several or more gases. Currently, commercial gas sensors are mostly selective for a single gas or sensor arrays are formed by a plurality of single component sensors, which greatly increases the cost and fails to meet the requirement of testing multiple mixed components.
A generally ideal gas sensor should have the following characteristics: (1) The response speed is high, and the response speed is generally required to be less than 50s (comprising two processes of gas adsorption and desorption); (2) The sensitivity is high, and only the high sensitivity can be sensitive to a small amount of gas concentration; (3) The method has high selectivity, is only sensitive to certain specific gases, and is not sensitive to other gases; (4) Reversibility, repeated sensitivity, that is, non-disposable sensitivity, and long-term repeated use; (5) The service life is long, and half year or more than one year is generally required; and (6) the size is small, and the installation and the carrying are convenient.
The physical interface between two different materials is commonly referred to as a heterojunction, whereas materials that combine the two different components have a heterostructure. The conductivity type of both sides of the junction is controlled by doping, the same doping type is called homoheterojunction (n-n, p-p), and the different doping type is called heteroheterojunction (n-p, p-n). The homoheterojunction is a majority carrier device, has higher speed than a few carrier devices, and is suitable for being used as a gas sensor. Most of the existing similar gas sensors can only detect single specific gas, can not realize that one chip can detect multiple gases simultaneously and specifically, and the existing heterostructure gas sensors can not simultaneously meet the switching between independent testing of single components and heterojunction forming testing, and are single in function and high in cost.
Disclosure of Invention
Therefore, the technical problems to be solved by the invention are to solve the problems that a single chip cannot detect multiple gases simultaneously and specifically and a traditional heterostructure type gas sensor cannot simultaneously meet the switching between independent testing of a single component and heterojunction forming testing, and the invention has single function, high cost and the like.
In order to solve the technical problems, the invention provides a gas sensor and a preparation method and application thereof. Based on a single chip, the MEMS processing technology is utilized, the multifunctional patterned multilayer thin film heterostructure is designed, and the specificity detection of various gases can be simultaneously realized through the switching of the output electrode, and the multifunctional patterned multilayer thin film heterostructure has higher sensitivity.
A first object of the present invention is to provide a gas sensor comprising a substrate, the surface of which is further provided with GeTeO x A film and an elemental co-doped CuO film; the GeTeO is x The middle part of the film and the element co-doped CuO film are overlapped and form a heterostructure, the GeTeO x The film and the part of the CuO film co-doped with the element extend to the substrate, the GeTeO x The end parts of the film and the CuO film co-doped with the elements are provided with conductive metal films, wherein 0<x≤4。
In one embodiment of the present invention, the GeTeO x The two ends of the film and the CuO film co-doped with the elements are respectively provided with 0-2 conductive metal films, the GeTeO x At least 1 conductive metal film is arranged on the film and the element co-doped CuO film.
In one embodiment of the present invention, the GeTeO x The overlapping part of the film and the CuO film co-doped with the elements is in an interdigital structure.
In one embodiment of the invention, the material of the matrix is Si.
In one embodiment of the present invention, the CuO thin film is doped with two or more of Y, W, sn, al, in and Ni.
In one embodiment of the invention, the conductive metal is one or more of Au, ag, cr, pt, pd, ti, al, W.
In one embodiment of the invention, the gas sensor can meet the requirements of high-sensitivity and high-selectivity gas detection by optimizing relevant parameters such as material composition, film thickness and the like.
In one embodiment of the invention, the patterned interdigital structure in the gas sensor can continuously drip sensitive materials, so that new heterostructure construction can be easily realized, and more gas can be detected.
In one embodiment of the invention, the gas sensor is arranged in an interdigital configuration.
In one embodiment of the invention, zinc oxide nano material can be also introduced to form a p-n heterostructure to detect H 2 And (3) gas.
A second object of the present invention is to provide a method for manufacturing a gas sensor, comprising the steps of,
s1, etching an electrode channel on the surface of a pretreated substrate, and sputtering a conductive metal film on the electrode channel;
s2, sputtering GeTeO on the surface of the substrate x Film, sputtering gas is mixed gas of argon and oxygen, wherein 0<x≤4；
S3, at the GeTeO x Sputtering an element co-doped CuO film on the surface of the film, wherein the element co-doped CuO film extends to the surface of the substrate, and the sputtering gas is argon;
s4, at the GeTeO x And sputtering a conductive metal film on the surface of a non-overlapped part of the film and the element co-doped CuO film to obtain the gas sensor.
In one embodiment of the present invention, in step S1, the pretreatment is ultrasonic cleaning with acetone, ethanol and deionized water in sequence.
In one embodiment of the present invention, in step S1, the etching is to prepare a specific electrode pattern by using a photoresist-photolithography-developing process, and then make a shallow electrode channel by using a reactive ion etcher.
In one embodiment of the inventionWherein the sputtering is vapor deposition, and the vacuum degree is less than 1.0X10 - 3 Pa。
In one embodiment of the invention, the power of the sputtering is 5-200W and the sputtering time is 1-30min.
In one embodiment of the invention, the flow rate of the gas is 1-50sccm and the sputtering pressure of the gas is 0.5-10Pa.
A third object of the present invention is to provide a gas sensor for detecting H 2 S、NH 3 Or NO 2 Is used in the field of applications.
In one embodiment of the invention, the temperature detected in the application is 50-300℃and the concentration of gas is 1-200ppm.
In one embodiment of the invention, the switching between the independent test of a single component and the test for forming the heterojunction can be simultaneously satisfied through the structure optimization design, thereby realizing multifunctionality and greatly reducing the cost.
Compared with the prior art, the technical scheme of the invention has the following advantages:
(1) GeTeO in the gas sensor x The film itself is opposite to H 2 S has better selectivity and sensitivity, and the CuO film co-doped with the elements has NO 2 Has good selectivity and sensitivity, geTeO x The method can form a heterostructure with an element doped CuO film, a built-in electric field is formed at the interface of two film materials, separation of carriers can be promoted, meanwhile, an active adsorption site formed at the interface is higher than other positions, gas molecules tend to interact with the materials at the interface, electron exchange is generated, electrons or holes of the materials are increased, transport of the carriers is promoted under the action of the built-in electric field, and meanwhile, the sensitivity and selectivity of a gas sensor can be greatly improved due to the fact that the polarity, the size, the structure and the like of the gas molecules are different, for example, a heterojunction interface formed by two materials in the invention is opposite to NH 3 Exhibits excellent selectivity and sensitivity.
(2) The multifunctional patterned multilayer thin film heterostructure chip in the gas sensor can specifically detect various gases by connecting different electrode points, and can be further used as an interdigital electrode to drop or sputter sensitive materials to form a new heterostructure, so that the specific detection of more gases is realized.
(3) The gas sensor pair H of the invention 2 S、NH 3 、NO 2 Has high sensitivity and lower detection limit. The higher the test temperature, the lower the detection limit and the higher the sensitivity. In addition, the thin film electrode product adopts a hard template method to form an interdigital electrode structure, so that the dripping of other gas sensitive materials can be further carried out, a new gas sensitive material can be flexibly introduced to construct a new heterostructure, and the functions of the device are more diversified. The invention has simple operation and simple reaction condition, and the magnetron sputtering method has low price and uniform film formation, can be used for preparing the vessel sensor components on a large scale, and is suitable for industrial production.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which:
FIG. 1 is a flow chart of the preparation of a gas sensor in an embodiment of the invention.
Fig. 2 is a physical diagram of a gas sensor in example 1 of the present invention.
Fig. 3-8 are response-recovery curves for different gases from different gas sensors in the test examples of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and specific examples, which are not intended to be limiting, so that those skilled in the art will better understand the invention and practice it.
Example 1
Referring to fig. 1, a gas sensor and a method for manufacturing the same specifically include the steps of:
s1, etching an electrode channel on the surface of a Si substrate after ultrasonic cleaning sequentially by using acetone, ethanol and deionized water;
S2、sputtering an Al film on the electrode channel by adopting a vapor deposition method; the vacuum degree of the chamber is 8.0X10 -4 Pa; the sputtering power is 20W, and the sputtering time is 3min;
s3, sputtering GeTeO on the surface of the substrate by adopting a vapor deposition method x (x is more than or equal to 1 and less than or equal to 3), wherein sputtering gas is mixed gas of 15sccm argon and 10sccm oxygen; sputtering power is 50W and 100W; sputtering air pressure is 1.0Pa; sputtering time is 5min;
s4, adopting a vapor deposition method to prepare GeTeO x Sputtering Y, W co-doped CuO film on the surface of the film, and extending the film to the surface of the substrate, wherein sputtering gas is 30sccm of argon; the sputtering power is respectively 10W, 20W and 40W; sputtering air pressure is 1.0Pa; sputtering time is 3min;
s5, adopting a vapor deposition method to prepare GeTeO x Sputtering an Al film on the surface of a non-overlapped part of the film and the Y, W co-doped CuO film; the sputtering power was 20W and the sputtering time was 3min, resulting in the gas sensor shown in fig. 2.
Example 2
A gas sensor and a preparation method thereof specifically comprise the following steps:
s1, etching an electrode channel on the surface of a Si substrate after ultrasonic cleaning sequentially by using acetone, ethanol and deionized water;
s2, sputtering an Au film on the electrode channel by adopting a vapor deposition method; the vacuum degree of the chamber is 8.0X10 -4 Pa; the sputtering power is 20W, and the sputtering time is 3min;
s3, sputtering GeTeO on the surface of the substrate by adopting a vapor deposition method x (x is more than or equal to 2 and less than or equal to 4), wherein sputtering gas is mixed gas of 10sccm argon and 20sccm oxygen; sputtering power is 50W and 100W; sputtering time is 5min;
s4, adopting a vapor deposition method to prepare GeTeO x Sputtering Y, W co-doped CuO film on the surface of the film, and extending the film to the surface of the substrate, wherein sputtering gas is 30sccm of argon; the sputtering power is respectively 10W, 20W and 40W; sputtering time is 3min;
s5, adopting a vapor deposition method to prepare GeTeO x Sputtering and sputtering Au films on the surfaces of non-overlapped parts of the films and the Y, W co-doped CuO films; the sputtering power was 20W and the sputtering time was 3min.
Example 3
A gas sensor and a preparation method thereof specifically comprise the following steps:
s1, etching an electrode channel on the surface of a Si substrate after ultrasonic cleaning sequentially by using acetone, ethanol and deionized water;
s2, sputtering a Pt film on the electrode channel by adopting a vapor deposition method; the vacuum degree of the chamber is 8.0X10 -4 Pa; the sputtering power is 20W, and the sputtering time is 3min;
s3, sputtering GeTeO on the surface of the substrate by adopting a vapor deposition method x (x is more than or equal to 1 and less than or equal to 3), wherein sputtering gas is mixed gas of 10sccm argon and 15sccm oxygen; sputtering power is 50W and 100W; sputtering time is 5min;
s4, adopting a vapor deposition method to prepare GeTeO x Sputtering a CuO film co-doped with Al and In on the surface of the film, and extending the CuO film to the surface of a substrate, wherein sputtering gas is 30sccm of argon; sputtering power is respectively 20W, 20W and 40W; sputtering time is 3min;
s5, adopting a vapor deposition method to prepare GeTeO x Sputtering Pd film on the non-overlapped part surface of the film and the Al and In co-doped CuO film; the sputtering power was 20W and the sputtering time was 3min.
Comparative example 1
S1, etching an electrode channel on the surface of a Si substrate after ultrasonic cleaning sequentially by using acetone, ethanol and deionized water;
s2, sputtering an Au film on the electrode channel by adopting a vapor deposition method; the vacuum degree of the chamber is 8.0X10 -4 Pa, the sputtering power is 20W, and the sputtering time is 3min;
s3, sputtering GeTeO on the surface of the substrate by adopting a vapor deposition method x (x is more than or equal to 1 and less than or equal to 3), wherein sputtering gas is mixed gas of 5sccm argon and 25sccm oxygen; sputtering power is 50W and 100W; sputtering time is 2min;
s4, adopting a vapor deposition method to prepare GeTeO x Sputtering Y, W co-doped CuO film on the surface of the film, and extending the film to the surface of the substrate, wherein sputtering gas is 30sccm of argon; the sputtering power is respectively 10W, 20W and 40W; sputtering time is 3min;
s5, adopting a vapor deposition method to prepare a film on the surface of the substrate GeTeO x Sputtering Au film on the non-overlapped part surface of the film and the Y, W co-doped CuO film; the sputtering power was 20W and the sputtering time was 3min.
Comparative example 2
S1, etching an electrode channel on the surface of a Si substrate after ultrasonic cleaning sequentially by using acetone, ethanol and deionized water;
s2, sputtering an Au film on the electrode channel by adopting a vapor deposition method; the vacuum degree of the chamber is 8.0X10 -4 Pa, the sputtering power is 20W, and the sputtering time is 3min;
s3, sputtering GeTeO on the surface of the substrate by adopting a vapor deposition method x (x is more than or equal to 1 and less than or equal to 3), wherein sputtering gas is mixed gas of 10sccm argon and 15sccm oxygen; sputtering power is 50W and 100W; sputtering time is 5min;
s4, adopting a vapor deposition method to prepare GeTeO x Sputtering Y, W co-doped CuO film on the surface of the film, and extending the film to the surface of the substrate, wherein sputtering gas is mixed gas of 20sccm oxygen and 10sccm argon; the sputtering power is respectively 10W, 20W and 40W; sputtering time is 3min;
s5, adopting a vapor deposition method to prepare GeTeO x Sputtering Au film on the non-overlapped part surface of the film and the Y, W co-doped CuO film; the sputtering power was 20W and the sputtering time was 3min.
Comparative example 3
S1, etching an electrode channel on the surface of a Si substrate after ultrasonic cleaning sequentially by using acetone, ethanol and deionized water;
s2, sputtering an Au film on the electrode channel by adopting a vapor deposition method; the vacuum degree of the chamber is 8.0X10 -4 Pa, the sputtering power is 20W, and the sputtering time is 3min;
s3, sputtering GeTeO on the surface of the substrate by adopting a vapor deposition method x (x is more than or equal to 1 and less than or equal to 3), wherein sputtering gas is mixed gas of 10sccm argon and 15sccm oxygen; sputtering power is 50W and 100W; sputtering time is 5min;
s4, adopting a vapor deposition method to prepare GeTeO x Sputtering Y, W co-doped CuO film on the surface of the film, extending the film to the surface of the substrate, wherein sputtering gas is 30sccm of argon; the sputtering power is respectively 10W, 10W and 40W; sputtering time is 3min;
s5, adopting a vapor deposition method to prepare GeTeO x Sputtering Au film on the non-overlapped part surface of the film and the Y, W co-doped CuO film; the sputtering power was 20W and the sputtering time was 3min.
Test example 1
The device obtained in example 1 (see FIG. 2 for a physical diagram), as shown in FIG. 1 (4), the 4 and 5 electrodes of the sensor device were connected to a dynamic gas test system, the test voltage was set to 1V, the dry air was used as a background gas and a diluent gas, the device was purged with the dry air and heated to 200℃before the target gas (the gas to be tested) was introduced, while the current-time change curve was recorded by continuous test, and when the baseline was leveled, NO with a concentration of 10ppm was emitted 2 After the gas is introduced into the test cavity for 60 seconds, the dry air is used for purging for 600 seconds, and the process is repeated for 6 times, so that the gas-sensitive material pair corresponding to the 4 electrode and the 5 electrode is obtained 2 Response-recovery curve of gas, through response formula s= (|i) t -I 0 |)/I 0 Calculate its response, where S is the response value, I t For the current value of the device in the target gas, I 0 To dry the current values of the devices in air, a response-time curve as shown in fig. 3 was obtained. FIG. 3 shows YW-co-doped CuO film vs. 10ppm NO 2 The response sensitivity of the gas is high, about 5.0, and the recovery performance is good.
Test example 2
The device obtained in comparative example 1 was subjected to a dynamic gas test system with 2 and 3 electrodes of the sensor device set at 1V as shown in FIG. 1 (4), and dry air was used as a background gas and a diluent gas, and the device was purged with dry air and heated to 200℃before the target gas (gas to be measured) was introduced, while continuing the test to record the current-time variation curve, and when the baseline was leveled, NO at a concentration of 10ppm was supplied 2 After the gas is introduced into the test cavity for 60s, the process is purged for 600s by dry air, and is repeated for 4 times, so that the gas-sensitive material corresponding to the 2 electrode and the 3 electrode is obtained for 10ppm NO 2 Response-recovery curve of gas, through response formula s= (|i) t -I 0 |)/I 0 Calculate its response, where S is the response value, I t For devices in a target gasCurrent value, I 0 To dry the current values of the devices in air, a response-time curve as shown in fig. 4 was obtained. GeTeO is shown in FIG. 4 x Film pair 10ppmNO 2 The response sensitivity of the gas 4 times repeated response-recovery curve is very poor and is about 0.03, and the baseline shifts upwards due to poor recovery performance.
Test example 3
The device obtained in comparative example 2 was subjected to a dynamic gas test system with the electrodes 4 and 5 of the sensor device set at 1V as shown in FIG. 1 (4), and dry air was used as a background gas and a diluent gas, and the device was purged with dry air and heated to 200℃before the target gas (gas to be measured) was introduced, while continuing the test to record the current-time variation curve, and when the baseline was leveled, H at a concentration of 10ppm was measured 2 S gas is introduced into the test cavity for 60S and then is purged for 600S by dry air, thus obtaining the gas-sensitive material pair corresponding to the 4 electrode and the 5 electrode of 10ppm H 2 Response-recovery curve of S gas, by the response formula s= (|i) t -I 0 |)/I 0 Calculate its response, where S is the response value, I t For the current value of the device in the target gas, I 0 To dry the current values of the devices in air, a response-time curve as shown in fig. 5 was obtained. FIG. 5 shows YW-co-doped CuO film vs. 10ppm H 2 The response-recovery curve of S gas has a response sensitivity of about 0.75 and poor recovery performance.
Test example 4
The device obtained in example 1 was put in a dynamic gas test system with 2 and 3 electrodes of the sensor device as shown in FIG. 1 (4), the test voltage was set to 1V, the dry air was used as a background gas and a diluent gas, the device was purged with dry air and heated to 200℃before the target gas (gas to be tested) was introduced, while the current-time change curve was recorded by continuous test, and when the baseline was leveled, H at a concentration of 10 to 50ppm was measured 2 S gas is sequentially introduced into the test cavity for 60S and then is purged for 600S by dry air, so that the gas-sensitive material pair corresponding to the 2 electrode and the 3 electrode is obtained for 10ppm H 2 Response-recovery curve of S gas, by the response formula s= (|i) t -I 0 |)/I 0 Calculate its response, whichWherein S is a response value, I t For the current value of the device in the target gas, I 0 To dry the current values of the devices in air, a response-time curve as shown in fig. 6 was obtained. GeTeO is shown in FIG. 6 x Film pairs 10-50ppm H 2 And the response-recovery curve of the S gas has good response sensitivity and excellent recovery performance, and the baseline does not drift upwards.
Test example 5
The device obtained in example 2 was put in a dynamic gas test system with 2 and 3 electrodes of the sensor device as shown in FIG. 1 (4), the test voltage was set to 1V, the dry air was used as a background gas and a diluent gas, the device was purged with dry air and heated to 200℃before the target gas (gas to be tested) was introduced, while the current-time change curve was recorded by continuous test, and when the baseline was leveled, H at a concentration of 10 to 40ppm was measured 2 S gas is introduced into the test cavity for 60S and then is purged for 600S by dry air, thus obtaining the gas-sensitive material pair corresponding to the 2 electrode and the 3 electrode of 10-40ppm H 2 Response-recovery curve of S gas, by the response formula s= (|i) t -I 0 |)/I 0 Calculate its response, where S is the response value, I t For the current value of the device in the target gas, I 0 To dry the current values of the devices in air, a response-time curve as shown in fig. 7 was obtained. GeTeO is shown in FIG. 7 x Film pairs 10-40ppm H 2 And the response-recovery curve of the S gas has high response sensitivity and good recovery performance.
Test example 6
The device obtained in example 1 was subjected to a dynamic gas test system with electrodes 2, 6 or 4, 7 of the sensor device set at 1V, and dry air as background gas and diluent gas, and the device was purged with dry air and heated to 200deg.C before introducing the target gas (gas to be tested), while continuing the test to record the current-time variation curve, and when the baseline was leveled, NH at a concentration of 10-50ppm 3 After the gas is introduced into the test cavity for 60s, the gas is purged for 600s by dry air, and 10-50ppm NH of the gas sensitive material pair corresponding to the 2, 6 or 4, 7 electrodes is obtained 3 Response-recovery curve of gas, through response formula s= (|i) t -I 0 |)/I 0 Calculate its response, where S is the response value, I t For the current value of the device in the target gas, I 0 To dry the current values of the devices in air, a response-time curve as shown in fig. 8 was obtained. GeTeO is shown in FIG. 8 x YW-codoped CuO heterojunction film pair of 10-50ppm NH 3 The response-recovery curve of the gas has high response sensitivity and better recovery performance.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations and modifications of the present invention will be apparent to those of ordinary skill in the art in light of the foregoing description. It is not necessary here nor is it exhaustive of all embodiments. And obvious variations or modifications thereof are contemplated as falling within the scope of the present invention.
Claims (10)
1. A gas sensor comprises a matrix, wherein the surface of the matrix is also provided with GeTeO x A film and an elemental co-doped CuO film; the GeTeO is x The middle part of the film and the element co-doped CuO film are overlapped and form a heterostructure, the GeTeO x The film and the part of the CuO film co-doped with the element extend to the substrate, the GeTeO x The end parts of the film and the CuO film co-doped with the elements are provided with conductive metal films, wherein x is more than 0 and less than or equal to 4.
2. The gas sensor of claim 1, wherein the GeTeO x And 0-2 conductive metal films are respectively arranged at two ends of the film and the element co-doped CuO film.
3. The gas sensor of claim 1, wherein the GeTeO x The overlapping part of the film and the CuO film co-doped with the elements is in an interdigital structure.
4. The gas sensor of claim 1, wherein the substrate is Si.
5. The gas sensor according to claim 1, wherein the CuO thin film is doped with two or more of Y, W, sn, al, in and Ni.
6. The gas sensor of claim 1, wherein the conductive metal is one or more of Au, ag, cr, pt, pd, ti, al, W.
7. A method for preparing a gas sensor is characterized by comprising the following steps,
s1, etching an electrode channel on the surface of a pretreated substrate, and sputtering a conductive metal film on the electrode channel;
s2, sputtering GeTeO on the surface of the substrate x The film is sputtered by a mixed gas of argon and oxygen, wherein x is more than 0 and less than or equal to 4;
s3, at the GeTeO x Sputtering an element co-doped CuO film on the surface of the film, wherein the element co-doped CuO film extends to the surface of the substrate, and the sputtering gas is argon;
s4, at the GeTeO x And sputtering a conductive metal film on the surface of a non-overlapped part of the film and the element co-doped CuO film to obtain the gas sensor.
8. The method for manufacturing a gas sensor according to claim 7, wherein the sputtering power is 5-200W and the sputtering time is 1-30min.
9. The method for manufacturing a gas sensor according to claim 7, wherein the flow rate of the gas is 1-50sccm, and the sputtering pressure of the gas is 0.5-10Pa.
10. A gas sensor according to any one of claims 1 to 6 for detecting H 2 S、NH 3 Or NO 2 Is characterized in that the temperature detected in the application is 50-300 ℃,the concentration of the gas is 1-200ppm.
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