CN114487037A - Hydrogen sulfide gas sensor and preparation method and application thereof - Google Patents
Hydrogen sulfide gas sensor and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 11
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- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 2
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- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- NGCDGPPKVSZGRR-UHFFFAOYSA-J 1,4,6,9-tetraoxa-5-stannaspiro[4.4]nonane-2,3,7,8-tetrone Chemical compound [Sn+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O NGCDGPPKVSZGRR-UHFFFAOYSA-J 0.000 description 1
- 229910002704 AlGaN Inorganic materials 0.000 description 1
- 241000883964 Ariocarpus retusus Species 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- 229910002567 K2S2O8 Inorganic materials 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
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- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 description 1
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 description 1
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- 210000001533 respiratory mucosa Anatomy 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- FAKFSJNVVCGEEI-UHFFFAOYSA-J tin(4+);disulfate Chemical compound [Sn+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FAKFSJNVVCGEEI-UHFFFAOYSA-J 0.000 description 1
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- YQMWDQQWGKVOSQ-UHFFFAOYSA-N trinitrooxystannyl nitrate Chemical compound [Sn+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YQMWDQQWGKVOSQ-UHFFFAOYSA-N 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
Images
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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- Chemical Kinetics & Catalysis (AREA)
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- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
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Abstract
The invention discloses a hydrogen sulfide gas sensor and a preparation method and application thereof. The hydrogen sulfide gas sensor comprises a GaN substrate and a gas-sensitive layer, wherein the gas-sensitive layer comprises flower-shaped SnO2-SnO nanoparticles. The hydrogen sulfide gas sensor has simple structure, high responsivity and H pair2The S gas has high selectivity, and the adopted highly-dense laser light source can run more efficiently without being interfered by other external factors, has low power consumption, and can monitor low-concentration H at relatively low working temperature2S gas has very wide application prospect.
Description
Technical Field
The invention relates to the technical field of gas sensors, in particular to a hydrogen sulfide gas sensor and a preparation method and application thereof.
Background
Hydrogen sulfide (H)2S) is a colorless, inflammable, extremely toxic and pungent gas, is widely applied to petrochemical industry, and is an important chemical raw material. H2S has strong stimulation and corrosion effects on human mucosa, respiratory system, eyes and other tissues, so that the S can be used for treating H in air in important places such as factories, mines, parks and the like2S has very important significance in real-time monitoring and early warning. In recent years, oxide semiconductor-based H2S-sensitive materials (e.g. SnO2、ZnO、WO3CuO, NiO, etc.) have received wide attention, H2The research of S gas sensor has made great progress. However, existing H2The S gas sensor generally has the problems of complex design, high power consumption, low responsiveness, poor selectivity and the like, and is difficult to completely meet the requirements of practical application.
The GaN material has the advantages of wide forbidden band, excellent piezoresistive piezoelectric effect, good chemical stability and the like, can be applied to severe environments such as high temperature, strong radiation and the like, and the gas sensor based on the GaN material can work in the environment of 600 ℃, which is incomparable with devices developed by using traditional materials. However, although AlGaN/GaN heterostructure materials based on GaN materials have unique advantages in fabricating gas sensors that can operate in high temperature environments, research and understanding on GaN-based gas sensors is currently limited and sensing mechanisms and device fabrication are still under the stage of research and development.
Therefore, a device with simple structure, low power consumption, high responsiveness and H-pair function is developed2The GaN-based hydrogen sulfide gas sensor with high S gas selectivity has very important significance.
Disclosure of Invention
The invention aims to provide a hydrogen sulfide gas sensor and a preparation method and application thereof.
The technical scheme adopted by the invention is as follows:
a hydrogen sulfide gas sensor comprises a GaN substrate and a gas-sensitive layer, wherein the gas-sensitive layer comprises flower-shaped SnO2-SnO nanoparticles.
Preferably, the hydrogen sulfide gas sensor comprises a GaN substrate, a gas sensitive layer, a side electrode and a top electrode, wherein the gas sensitive layer is attached to one surface of the GaN substrate, the side electrode is attached to the GaN substrate, and the top electrode is attached to the gas sensitive layer.
Preferably, the hydrogen sulfide gas sensor comprises a GaN substrate, a gas sensitive layer, a side electrode, a top electrode and an etching layer, wherein the gas sensitive layer is attached to one surface of the GaN substrate, the side electrode is attached to the GaN substrate, the top electrode is attached to the gas sensitive layer, the etching layer is arranged on one surface, close to the gas sensitive layer, of the GaN substrate, and the etching layer is honeycomb-shaped.
Preferably, the side electrode is a gold electrode.
Preferably, the top electrode is a gold electrode.
Preferably, a substrate layer is further attached to one surface of the GaN base far away from the gas sensitive layer.
Preferably, the substrate layer is a sapphire layer.
Preferably, the flower-like SnO2The grain size of the-SnO nano-particles is 20-120 nm.
Preferably, the flower-like SnO2-SnO nanoparticles were prepared by the following method: dispersing urea and tin salt in water, transferring the water into a hydrothermal reaction kettle for hydrothermal reaction to obtain flower-shaped SnO2-SnO nanoparticles.
Further preferably, the flower-like SnO2-SnO nanoparticles were prepared by the following method: dispersing urea and tin salt in water, transferring into hydrothermal reaction kettle for hydrothermal reaction, centrifuging to obtain solid, washing with deionized water and anhydrous ethanol for several times, and drying to obtain flower-shaped SnO2-SnO nanoparticles.
Preferably, the molar ratio of the urea to the tin salt is 1: 0.5-0.8.
Preferably, the tin salt is tin chloride (SnCl)4) Tin oxalate (C)2O4Sn), sodium stannate (Na)2[Sn(OH)6]) Potassium stannate (K)2[Sn(OH)6]) Tin sulfate (Sn (SO)4)2) Tin nitrate (Sn (NO)3)4) At least one of (1).
Preferably, the hydrothermal reaction is carried out at 170-190 ℃ for 15-20 h.
Preferably, the thickness of the gas-sensitive layer is 700nm to 900 nm.
Preferably, the thickness of the etching layer is 0.2 μm to 1 μm.
The preparation method of the hydrogen sulfide gas sensor comprises the following steps:
1) forming a honeycomb-shaped etching layer on one surface of the GaN substrate by adopting a wet etching process;
2) flower-shaped SnO2-SnO nanoparticle dispersion coating on the waferEtching the surface of the layer to form a gas-sensitive layer;
3) and attaching the side electrode to the GaN substrate, and attaching the top electrode to the gas sensitive layer to obtain the hydrogen sulfide gas sensor.
Preferably, the etchant used in the wet etching process in step 1) is one of acid, alkali, neutral salt, amino acid, organic electrolyte and ionic liquid.
Further preferably, the etchant used in the wet etching process in step 1) is HF or H2C2O4、KOH、NaOH、EDTA-2Na、K2S2O8Alanine (Ala), valine (Val) and glycine (Gly).
The hydrogen sulfide gas detection device comprises the hydrogen sulfide gas sensor.
The working principle of the hydrogen sulfide gas sensor is as follows: in a general air environment, oxygen molecules in the air can be adsorbed on the surface of a gas-sensitive layer in a gas sensor, and at the moment, the oxygen molecules deprive electrons in a conduction band of the gas-sensitive layer so as to be converted into oxygen anions (O)-) In this process, a depletion layer is formed in the heterojunction of the gas sensor, resulting in an increase in the resistance of the gas sensor when hydrogen sulfide (H) is present2S) and the like, H2S and O-The reaction occurs and electrons are released into a depletion layer of a heterojunction of the gas sensor, so that the resistance of the gas sensor can be reduced, the conductivity of the gas sensor is increased, thereby generating a change in current signal, so that H can be detected2S gas, and the change of the current signal is along with H2S gas or O-The increase in concentration of (a) becomes more pronounced.
The invention has the beneficial effects that: the hydrogen sulfide gas sensor has simple structure, high responsivity and H pair2The S gas has high selectivity, and the adopted highly-dense laser light source can run more efficiently without being interfered by other external factors, has low power consumption, and can monitor low-concentration H at relatively low working temperature2S gas has very wide application prospect.
Drawings
Fig. 1 is a schematic structural view of a hydrogen sulfide gas sensor according to example 1.
Fig. 2 is an SEM image of the surface and cross section of the gas-sensitive layer in the hydrogen sulfide gas sensor of example 1.
Fig. 3 is a schematic structural view of the hydrogen sulfide gas sensor according to example 2.
Fig. 4 is a schematic structural view of a hydrogen sulfide gas sensor according to example 3.
Fig. 5 is an SEM image of the surface and cross section of an etching layer in the hydrogen sulfide gas sensor of example 3.
Fig. 6 is a schematic structural view of a hydrogen sulfide gas sensor according to example 4.
Fig. 7 is a graph showing the results of the selectivity test of the hydrogen sulfide gas sensor of example 4.
Fig. 8 is a graph showing the results of the response sensitivity test of the hydrogen sulfide gas sensor of example 4.
The attached drawings indicate the following:
10. a GaN substrate; 20. a gas-sensitive layer; 30. a side electrode; 40. a top electrode; 50. a substrate layer; 60. the layer is etched.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Flower-like SnO in examples 1 to 42The preparation method of the-SnO nano particles comprises the following steps:
0.108g of urea and 0.132g of SnCl4·2H2Adding O into 30mL of deionized water, stirring for 30min, transferring the obtained solution into a hydrothermal reaction kettle, reacting for 18h at 180 ℃, centrifuging, respectively centrifuging and washing the solid obtained by centrifuging for multiple times by using deionized water and absolute ethyl alcohol at the rotating speed of 2500rpm, and drying in an oven at 70 ℃ for 2 days to obtain the flower-shaped SnO2-SnO nanoparticles.
Example 1:
a hydrogen sulfide gas sensor (the structure schematic diagram is shown in figure 1) comprises a GaN substrate 10, a gas sensing layer 20, a side electrode 30 and a top electrode 40, wherein the gas sensing layer 20 is attached to one surface of the GaN substrate 10, the side electrode 30 is attached to the GaN substrate 10, and the top electrode 40 is attached to the gas sensing layer 20.
The preparation method of the hydrogen sulfide gas sensor comprises the following steps:
1) 100mg of flower-like SnO2Dispersing SnO nano particles into 5mL of ethanol to prepare dispersion liquid, and coating the dispersion liquid on the surface of a GaN substrate (single-side coating) to form a gas-sensitive layer;
2) and (3) evaporating a gold electrode on the GaN substrate as a side electrode, and evaporating a gold electrode on the gas sensitive layer as a top electrode to obtain the hydrogen sulfide gas sensor.
Scanning Electron Microscope (SEM) images of the surface and cross section of the gas-sensitive layer in the hydrogen sulfide gas sensor of this example are shown in fig. 2 (the main graph is the surface of the gas-sensitive layer, and the small graph at the upper right corner is the cross section of the gas-sensitive layer).
As can be seen from fig. 2: the gas-sensitive layer has an ordered and uniform pore distribution, a thickness of about 830nm and an average pore diameter of about 50 nm.
Example 2:
a hydrogen sulfide gas sensor (the structural schematic diagram is shown in FIG. 3) comprises a GaN substrate 10, a gas sensing layer 20, a side electrode 30, a top electrode 40 and a substrate layer 50, wherein the gas sensing layer 20 is attached to one surface of the GaN substrate 10, the side electrode 30 is attached to the GaN substrate 10, the top electrode 40 is attached to the gas sensing layer 20, and the substrate layer 50 is attached to one surface of the GaN substrate 10 far away from the gas sensing layer 20.
The preparation method of the hydrogen sulfide gas sensor comprises the following steps:
1) attaching a GaN substrate to the surface of the sapphire substrate;
2) 100mg of flower-like SnO2Dispersing SnO nano particles into dispersion liquid by using 5mL of ethanol, and coating the dispersion liquid on the surface of a GaN substrate to form a gas-sensitive layer;
3) and (3) evaporating a gold electrode on the GaN substrate as a side electrode, and evaporating a gold electrode on the gas sensitive layer as a top electrode to obtain the hydrogen sulfide gas sensor.
Example 3:
a hydrogen sulfide gas sensor (the schematic structural diagram is shown in FIG. 4) comprises a GaN substrate 10, a gas sensing layer 20, a side electrode 30, a top electrode 40 and an etching layer 60, wherein the gas sensing layer 20 is attached to one surface of the GaN substrate 10, the side electrode 30 is attached to the GaN substrate 10, the top electrode 40 is attached to the gas sensing layer 20, the etching layer 60 is arranged on one surface, close to the gas sensing layer 20, of the GaN substrate 10, and the etching layer 60 is honeycomb-shaped.
The preparation method of the hydrogen sulfide gas sensor comprises the following steps:
1) sequentially carrying out ultrasonic cleaning on the GaN substrate by using acetone, absolute ethyl alcohol and deionized water, and then using high-purity N2Blow drying, and then UV/O3Vacuum plasma processing (enhancing the hydrophilicity of the GaN substrate), placing the processed GaN substrate and the Pt sheet into hydrofluoric acid with the mass fraction of 40% as an anode and a cathode respectively, irradiating by a 300W xenon lamp, electrifying for etching (single-sided etching) to form an etching layer, wherein the etching voltage is 10V, the etching time is 10min, immersing the etched GaN substrate into oxalic acid solution with the concentration of 1mol/L, carrying out ultrasonic treatment for 30min, washing by deionized water, and then using N2Drying;
2) 100mg of flower-like SnO2Dispersing SnO nano particles into 5mL of ethanol to prepare dispersion liquid, and coating the dispersion liquid on the surface (etched surface) of the GaN substrate to form a gas-sensitive layer;
3) and (3) evaporating a gold electrode on the GaN substrate as a side electrode, and evaporating a gold electrode on the gas sensitive layer as a top electrode to obtain the hydrogen sulfide gas sensor.
SEM images of the surface and cross section of the etching layer in the hydrogen sulfide gas sensor of this example are shown in FIG. 5 (the main figure is the surface of the etching layer, and the small figure at the lower right is the cross section of the etching layer).
As can be seen from fig. 5: etching to form an uneven flower-shaped structure with the diameter of 20-120 nm on the surface of the GaN substrate, wherein the flower-shaped structure is formed by assembling nano sheets with the thickness of 8-10 nm and nano particles.
Example 4:
a hydrogen sulfide gas sensor (a structural schematic diagram is shown in FIG. 6) comprises a GaN substrate 10, a gas sensitive layer 20, a side electrode 30, a top electrode 40, a substrate layer 50 and an etching layer 60, wherein the gas sensitive layer 20 is attached to one surface of the GaN substrate 10, the side electrode 30 is attached to the GaN substrate 10, the top electrode 40 is attached to the gas sensitive layer 20, the substrate layer 50 is attached to one surface, far away from the gas sensitive layer 20, of the GaN substrate 10, the etching layer 60 is arranged on one surface, close to the gas sensitive layer 20, of the GaN substrate 10, and the etching layer 60 is in a honeycomb shape.
The preparation method of the hydrogen sulfide gas sensor comprises the following steps:
1) attaching a GaN substrate to the surface of the sapphire substrate;
2) sequentially carrying out ultrasonic cleaning on the GaN substrate by using acetone, absolute ethyl alcohol and deionized water, and then using high-purity N2Blow drying, and then UV/O3Performing vacuum plasma treatment (enhancing the hydrophilicity of the GaN substrate), placing the treated GaN substrate and the Pt sheet into hydrofluoric acid with the mass fraction of 40% as an anode and a cathode respectively, irradiating by a 300W xenon lamp, performing electric etching with the etching voltage of 10V and the etching time of 10min, immersing the etched GaN substrate into oxalic acid solution with the concentration of 1mol/L, performing ultrasonic treatment for 30min, washing by deionized water, and then washing by N2Drying;
3) 100mg of flower-like SnO2Dispersing the-SnO nano particles with 5mL of ethanol to prepare a dispersion liquid, and coating the dispersion liquid on the surface of the GaN substrate to form a gas-sensitive layer;
4) and (3) evaporating a gold electrode on the GaN substrate as a side electrode, and evaporating a gold electrode on the gas sensitive layer as a top electrode to obtain the hydrogen sulfide gas sensor.
And (3) performance testing:
1) the selectivity of the hydrogen sulfide gas sensor of example 4 was tested by the following steps: the gas sensor testing system WS-30B developed by Zhengzhou Weisheng electronic technology Co., Ltd is adopted for testing, the mass flow controller (MFC, Sevenstar CS200) is used for controlling the flow ratio of the testing gas/air to change the concentration of the testing gas, the testing gas flows at a constant rate of 400 standard cubic centimeters per minute (sccm) in the testing process, and all the testing gases (ethanol steam with the concentration of 50ppm, H steam and H steam) flow at a constant rate of 400 standard cubic centimeters per minute (sccm)2S、H2And NO2) Were all conducted at an operating temperature of 150 c and the selectivity test results are shown in figure 7.
Note:
the sensitivity (S) is calculated as: r ═ Sa/RgIn the formula, RaBase line resistance, R, for in air testinggThe resistance of the sensor obtained by testing in the target gas-air mixed gas is obtained.
As can be seen from fig. 7: hydrogen sulfide gas sensor of example 4 for ethanol vapor and H2S、H2And NO2The sensitivity values of (a) were 1.34, 6.21, 0.84 and 0.48, respectively, and it can be seen that the hydrogen sulfide gas sensor of example 4 is paired with H2The response of S is significantly higher than that of the other gases, indicating that the hydrogen sulfide gas sensor of example 4 is paired with H2The S gas has extremely high selectivity.
2) The response sensitivity of the hydrogen sulfide gas sensor of example 4 was tested by the following steps: the semiconductor analyzer (Model Keithley 2450, Keithley Instruments, USA) was used to test different concentrations of H with the aid of different light sources2The change in resistance of the hydrogen sulfide gas sensor in S, which was controlled by the KickStart software via the General Purpose Interface Bus (GPIB), gave the response sensitivity test results shown in fig. 8.
As can be seen from fig. 8: the hydrogen sulfide gas sensor of example 4 has the highest sensitivity with the aid of the ultraviolet laser light source, the next highest sensitivity with the aid of the LED light source, and the lowest sensitivity without the aid of any light source, which indicates that the hydrogen sulfide gas sensor of example 4 shows the ultrahigh response capability to the ultraviolet laser light source.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A hydrogen sulfide gas sensor, characterized by: the hydrogen sulfide gas sensor comprises a GaN substrate and a gas-sensitive layer; the gas-sensitive layer comprises flower-shaped SnO2-SnO nanoparticles.
2. The hydrogen sulfide gas sensor according to claim 1, wherein: the hydrogen sulfide gas sensor comprises a GaN substrate, a gas sensitive layer, a side electrode and a top electrode; the gas-sensitive layer is attached to one surface of the GaN substrate; the side electrode is attached to the GaN substrate; the top electrode is attached to the gas sensitive layer.
3. The hydrogen sulfide gas sensor according to claim 2, wherein: and a substrate layer is also attached to one surface of the GaN base, which is far away from the gas sensitive layer.
4. The hydrogen sulfide gas sensor according to claim 2, wherein: and a honeycomb-shaped etching layer is also arranged on one surface of the GaN substrate close to the gas sensitive layer.
5. The hydrogen sulfide gas sensor according to claim 4, wherein: and a substrate layer is also attached to one surface of the GaN base, which is far away from the gas sensitive layer.
6. The hydrogen sulfide gas sensor according to any one of claims 1 to 5, wherein: the flower-like SnO2The grain size of the-SnO nano-particles is 20-120 nm.
7. The hydrogen sulfide gas sensor according to any one of claims 1 to 5, wherein: the thickness of the gas-sensitive layer is 700 nm-900 nm.
8. The hydrogen sulfide gas sensor according to claim 4 or 5, wherein: the thickness of the etching layer is 0.2-1 μm.
9. The method of manufacturing a hydrogen sulfide gas sensor according to claim 4, comprising the steps of:
1) forming a honeycomb-shaped etching layer on one surface of the GaN substrate by adopting a wet etching process;
2) flower-like SnO2Coating the dispersion liquid of the-SnO nano particles on the surface of the etching layer to form a gas-sensitive layer;
3) and attaching the side electrode to the GaN substrate, and attaching the top electrode to the gas sensitive layer to obtain the hydrogen sulfide gas sensor.
10. A hydrogen sulfide gas detection device comprising the hydrogen sulfide gas sensor according to any one of claims 1 to 8.
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