CN113136547B - Tin dioxide oxide film, preparation method and application thereof in hydrogen detection - Google Patents

Tin dioxide oxide film, preparation method and application thereof in hydrogen detection Download PDF

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CN113136547B
CN113136547B CN202110402049.XA CN202110402049A CN113136547B CN 113136547 B CN113136547 B CN 113136547B CN 202110402049 A CN202110402049 A CN 202110402049A CN 113136547 B CN113136547 B CN 113136547B
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tin dioxide
sputtering
hydrogen
gas
film
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CN113136547A (en
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宋安刚
朱地
赵保峰
关海滨
徐丹
王树元
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Energy Research Institute of Shandong Academy of Sciences
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/08—Oxides
    • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/0021—Reactive sputtering or evaporation
    • C23C14/0036—Reactive sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/34—Sputtering
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment
    • 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

Abstract

The invention discloses a tin dioxide oxide film, a preparation method and application thereof in hydrogen detection, wherein the crystal phase structure of the tin dioxide oxide film is a rutile phase structure, the resistance before hydrogen is introduced is 80-100 omega at room temperature, and the resistance after hydrogen is 50-70 omega. The preparation method comprises the following steps: and preparing the tin into a deposited tin dioxide film by utilizing far-source plasma sputtering, and then carrying out annealing treatment to obtain a rutile tin dioxide film, wherein the obtained rutile tin dioxide film is the target tin dioxide oxide film. The tin dioxide oxide film provided by the invention can have good gas-sensitive performance to hydrogen at room temperature.

Description

Tin dioxide oxide film, preparation method and application thereof in hydrogen detection
Technical Field
The invention belongs to the technical field of film materials and hydrogen detection, and relates to a tin dioxide oxide film, a preparation method and application thereof in hydrogen detection.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Tin dioxide (SnO) 2 ) Is a metal oxide semiconductor that is very widely used as a gas sensor because it can be used to detect flammable gases such as methane, hydrogen, and carbon monoxide. In recent years, as the amount of liquefied petroleum gas and compressed natural gas used increases, the frequency of accidental explosions due to leakage increases. Therefore, monitoring and accurately measuring the leakage of explosive gases is critical to preventing such accidents from occurring. Gas sensor systems have been developed that can selectively detect and determine various combustible gases. Thus, a considerable part of the research activity at present has been devoted to the development of stable, pure or doped tin dioxide sensors. The tin dioxide gas sensor process mainly comprises chemical adsorption and surface chemical reaction under the participation of lattice oxygen. Pre-adsorption meterSurface reactions between the surface oxygen and the reducing gas can result in n-type SnO 2 The electrical conductivity of (b) is changed, and thus the change in resistance can be used to detect various gases having reducibility.
Many methods have been adopted by researchers to modify the characteristics of these semiconductor oxide gas sensors to achieve high sensitivity and selectivity, such as using different additives to increase the response rate and selectivity to a single gas, using physical or chemical filters to enhance the reaction rate of less sensitive gases or to regulate different operating temperatures, etc.
According to the research of the inventor, the current tin dioxide gas sensor needs to detect hydrogen under the condition of high temperature (more than 100 ℃) in the detection of the hydrogen, and the gas sensor mainly plays a role in detecting the components of the gas. The hydrogen is used as clean energy and has excellent application prospect, and the temperature of the hydrogen during storage or use cannot reach more than 100 ℃, so that the existing tin dioxide gas sensor cannot detect the storage of the hydrogen, thereby hindering the popularization and application of the tin dioxide gas sensor.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide a tin dioxide oxide film, a preparation method and application thereof in detecting hydrogen.
In order to achieve the purpose, the technical scheme of the invention is as follows:
on the one hand, the crystal phase structure of the tin dioxide oxide film is a rutile phase structure, the resistance before hydrogen is introduced is 80-100 omega at room temperature, and the resistance after hydrogen is 50-70 omega.
When the tin dioxide is contacted with hydrogen, the oxygen with negative charges adsorbed on the surface of the tin dioxide reacts with the hydrogen, released electrons are transferred to a conduction band of a tin dioxide crystal grain again, so that the conductivity of the tin dioxide is increased, the resistance is reduced, and the sensitivity detection on the hydrogen is realized through the reduction of the resistance. Thus, the factors influencing the performance of tin dioxide sensitive to hydrogen are mainly: 1. the resistivity of tin dioxide itself, 2. the rate of reaction of negatively charged oxygen on the surface of tin dioxide with hydrogen. If the reaction rate of the oxygen negatively charged on the surface of tin dioxide with hydrogen is too low when the resistance of tin dioxide is too high, the resistance change is not obvious. Therefore, the tin dioxide gas sensor in the prior art basically increases the reaction rate of oxygen with negative charges on the surface of tin dioxide and hydrogen by raising the temperature, so that the resistance of tin dioxide is obviously changed, and the sensitivity detection on the hydrogen is realized.
The tin dioxide oxide film provided by the invention has low resistance at room temperature, and is only 80-100 omega; secondly, the microstructure of the sensor is beneficial to the increase of the reaction rate of oxygen with negative charges on the surface of the tin dioxide and hydrogen under the room temperature condition, so that the resistance is reduced to 50-70 omega after the hydrogen is introduced, and the reduction of the resistance is more obvious compared with the self low resistance, thereby realizing the sensitivity detection of the hydrogen at room temperature.
On the other hand, the preparation method of the tin dioxide oxide film utilizes far-source plasma sputtering to prepare tin into a deposited tin dioxide film, and then carries out annealing treatment to obtain the rutile phase tin dioxide film. The obtained rutile phase tin dioxide film is the target tin dioxide oxide film.
According to the method, the resistance of the tin dioxide film is reduced, the resistance at room temperature is only 80-100 omega, and the reaction rate of oxygen with negative charges on the surface of the tin dioxide and hydrogen can be increased by the formed special microstructure under the room temperature condition, so that the resistance is reduced to 50-70 omega after the hydrogen is introduced, the resistance change is more obvious, and the sensitivity detection on the hydrogen at room temperature is realized.
In a third aspect, the use of the tin dioxide oxide film in detecting hydrogen is provided.
In a fourth aspect, a hydrogen gas sensor comprises a gas sensitive element and a fixing frame, wherein the gas sensitive element is mounted on the fixing frame, and the gas sensitive element is the tin dioxide oxide film.
In a fifth aspect, a method for detecting hydrogen gas is provided, wherein a gas to be detected containing hydrogen gas is passed through the tin dioxide oxide thin film, and a change in resistance of the tin dioxide oxide thin film is detected.
The invention has the beneficial effects that:
1. according to the invention, the far-source plasma sputtering and annealing treatment are adopted, so that the resistance of the tin dioxide film is reduced, a special microstructure can be formed, the reaction rate of oxygen with negative charges on the surface of the tin dioxide film and hydrogen can be increased under the room temperature condition, and the tin dioxide film can generate a gas-sensitive effect on the hydrogen at room temperature.
2. The preparation method has the advantages of high sputtering speed, low sputtering temperature, good repeatability, low energy consumption and low production cost, and is suitable for popularization and application.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a rutile phase SnO comprising examples 1, 2, 3 2 X-ray diffraction patterns of the film at different annealing temperatures;
FIG. 2 is a diagram of the as-deposited SnO prepared in comparative example 1 2 An X-ray diffraction pattern of the film;
FIG. 3 shows rutile phase SnO of experimental example 2 Scanning electron microscope atlas of the film under different magnification;
FIG. 4 shows rutile phase SnO of experimental example 2 High resolution transmission electron microscopy spectra of the film;
FIG. 5 shows rutile phase SnO of experimental example 2 EDS energy spectrum of the film;
FIG. 6 shows rutile phase SnO of experimental example 2 XPS spectra of Sn3d for the films;
FIG. 7 shows rutile phase SnO of experimental example 2 XPS spectra of O1s for films;
FIG. 8 shows rutile phase SnO of experimental example 2 Gas-sensitive spectra of the film;
FIG. 9 shows experimental examples of as-deposited SnO 2 Of filmsGas-sensitive spectrum.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
In view of the difficulty in detecting hydrogen at room temperature of the existing tin dioxide gas sensor, the invention provides a tin dioxide oxide film, a preparation method and application thereof in hydrogen detection.
The invention provides a tin dioxide oxide film, wherein a crystal phase structure is a rutile phase structure, the resistance before hydrogen is introduced is 80-100 omega at room temperature, and the resistance after hydrogen is 50-70 omega.
The tin dioxide oxide film provided by the invention has low resistance at room temperature, and is only 80-100 omega; secondly, the microstructure of the sensor is beneficial to the increase of the reaction rate of oxygen with negative charges on the surface of the tin dioxide and hydrogen under the room temperature condition, so that the resistance is reduced to 50-70 omega after the hydrogen is introduced, and the reduction of the resistance is more obvious compared with the self low resistance, thereby realizing the sensitivity detection of the hydrogen at room temperature.
The room temperature refers to the temperature of an indoor environment, and is generally 15-30 ℃.
In some examples of this embodiment, the resistance before the hydrogen gas is introduced is 80-85 Ω.
In some examples of this embodiment, the resistance after the hydrogen gas is introduced is 65 to 70 Ω.
In another embodiment of the invention, a method for preparing a tin dioxide oxide film is provided, wherein tin is prepared into a deposited tin dioxide film by using far-source plasma sputtering, and then annealing treatment is carried out to obtain a rutile tin dioxide film. The obtained rutile phase tin dioxide film is the target tin dioxide oxide film.
According to the method, the resistance of the tin dioxide film is reduced, the resistance at room temperature is only 80-100 omega, and the reaction rate of oxygen with negative charges on the surface of the tin dioxide and hydrogen can be increased by the formed special microstructure under the room temperature condition, so that the resistance is reduced to 50-70 omega after the hydrogen is introduced, the resistance change is more obvious, and the sensitivity detection on the hydrogen at room temperature is realized.
In addition, experiments show that the deposited tin dioxide prepared by only utilizing far-source plasma sputtering has no gas sensitivity to hydrogen at room temperature, and only the rutile-phase tin dioxide film prepared after annealing has the gas sensitivity to hydrogen.
In some examples of this embodiment, the annealing temperature is 300 to 500 ℃. Can ensure that the deposited tin dioxide is completely converted into rutile tin dioxide, and the formed micro morphology is more beneficial to increasing the reaction rate of oxygen with negative charges on the surface of the tin dioxide and hydrogen under the room temperature condition.
In some examples of this embodiment, the oxygen is a reactive gas and the flow rate of the oxygen is 1-10 sccm (standard milliliters per minute). The oxygen is preferably a high purity gas having a purity of not less than 99.999%.
In some examples of this embodiment, argon is the plasma source gas in remote source plasma sputtering. The flow rate of the argon gas is 50-100 sccm. The argon gas is preferably a high purity gas having a purity of not less than 99.999%.
In some examples of this embodiment, the power of the plasma emission source is 300-500W during the remote plasma sputtering.
In some examples of this embodiment, the target accelerating bias power is 50-100W in the remote plasma sputtering.
In some examples of this embodiment, the pressure in the sputtering chamber is 2-5 × 10 during the remote plasma sputtering -3 mbar。
In some examples of this embodiment, the sputtering speed is 10-50 nm/min and the sputtering time is 10-20 min in the remote plasma sputtering.
In some examples of this embodiment, the sputtering temperature is 20-50 ℃ and the substrate temperature is normal temperature in the remote plasma sputtering. The process of reactive sputtering deposition of the film is carried out at normal temperature or lower temperature, the substrate does not need to be heated, and the sputtering process is simpler and easy to control. The normal temperature is a common temperature, and is usually 24-26 ℃.
The invention adopts far-source plasma sputtering to carry out reactive sputtering, which means that oxygen is continuously introduced as reaction gas in the sputtering process, the oxygen is combined with sputtered target particles in the air and reacts, under the action of an accelerating bias voltage provided for the bottom of the target, the oxygen flies to a substrate in the form of reaction products and is adhered to the surface of the substrate, and a layer of compact nano film is formed by deposition.
The substrate is a glass substrate. The glass substrate is cleaned before use, wherein the cleaning refers to that the glass substrate is sequentially placed in acetone, isopropyl ketone, ethanol and deionized water for ultrasonic cleaning, the cleaning time is 15min each time, and the cleaning temperature is 50 ℃. And drying by a nitrogen gun or wiping by a dust-free cloth after cleaning, and putting into a sputtering cavity of a remote source plasma sputtering system for sputtering. Before reactive sputtering, the sputtering cavity is vacuumized. Then argon gas with a certain flow is introduced into the cavity, and oxygen is introduced after the pressure in the cavity is kept stable.
In a third embodiment of the present invention, there is provided a use of the tin dioxide oxide thin film described above in detecting hydrogen.
In a fourth embodiment of the present invention, a hydrogen gas sensor is provided, which includes a gas sensitive element and a fixing frame, wherein the gas sensitive element is mounted on the fixing frame, and the gas sensitive element is the above tin dioxide oxide film.
In a fifth embodiment of the present invention, a method for detecting hydrogen is provided, in which a gas to be detected containing hydrogen is passed through the tin dioxide oxide thin film, and a change in resistance of the tin dioxide oxide thin film is detected.
In order to make the technical scheme of the present invention more clearly understood by those skilled in the art, the technical scheme of the present invention will be described in detail below by combining specific examples and comparative examples.
In a specific embodiment, the target used is a tin target with a size of 3 inches in diameter and 6mm in thickness.
Example 1
Rutile phase SnO of this example 2 The preparation method of the film comprises the following steps:
1) cleaning the glass substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 2 x 10 -6 mbar, introducing argon of 80sccm into the cavity, and starting a plasma source emission system after the pressure in the cavity is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the target to be bombarded by the plasma, and pre-sputtering the target;
introducing oxygen into the chamber, wherein the flow rate of the oxygen is 10sccm, and the pressure in the sputtering chamber is 4 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the reactive sputtering process, the power of a plasma emission source is 500W, the accelerating bias power of a target material is 100W, the sputtering speed is 20nm/min, the sputtering time is 20min, the sputtering temperature is 20 ℃, and the temperature of a glass substrate is normal temperature;
wherein the sputtering target is a tin target (the purity is 5N);
after the reactive sputtering is finished, closing a baffle plate below the glass substrate, and depositing a layer of nano film on the glass substrate to obtain a semi-finished product;
2) placing the semi-finished product obtained in the step 1) in a rapid annealing furnace under the air atmosphere condition, performing rapid annealing treatment at the temperature of 300 ℃ for 1 hour, and naturally cooling to room temperature to obtain the rutile phase SnO 2 A film.
Example 2
Rutile phase SnO of this example 2 The preparation method of the film comprises the following steps:
1) cleaning the glass substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 2 x 10 -6 mbar, introducing argon of 80sccm into the cavity, and starting a plasma source emission system after the pressure in the cavity is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the target to be bombarded by the plasma, and pre-sputtering the target;
introducing oxygen into the chamber with a flow rate of 10sccm and a pressure of 4 × 10 in the sputtering chamber -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%;after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the reactive sputtering process, the power of a plasma emission source is 500W, the accelerating bias power of a target material is 100W, the sputtering speed is 20nm/min, the sputtering time is 20min, the sputtering temperature is 20 ℃, and the temperature of a glass substrate is normal temperature;
wherein the sputtering target is a tin target (the purity is 5N);
after the reactive sputtering is finished, closing a baffle plate below the glass substrate, and depositing a layer of nano film on the glass substrate to obtain a semi-finished product;
2) placing the semi-finished product obtained in the step 1) in a rapid annealing furnace under the air atmosphere condition, performing rapid annealing treatment at 400 ℃ for 1 hour, and naturally cooling to room temperature to obtain the rutile phase SnO 2 A film.
Example 3
Rutile phase SnO of this example 2 The preparation method of the film comprises the following steps:
1) cleaning the glass substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
3) sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 2 x 10 -6 mbar, introducing argon of 80sccm into the cavity, and starting a plasma source emission system after the pressure in the cavity is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the target to be bombarded by the plasma, and pre-sputtering the target;
into the chamberOxygen is introduced, the flow rate of the oxygen is 10sccm, and the pressure in the sputtering cavity is 4 multiplied by 10 -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the reactive sputtering process, the power of a plasma emission source is 500W, the accelerating bias power of a target material is 100W, the sputtering speed is 20nm/min, the sputtering time is 20min, the sputtering temperature is 20 ℃, and the temperature of a glass substrate is normal temperature;
wherein the sputtering target is a tin target (the purity is 5N);
after the reactive sputtering is finished, closing a baffle plate below the glass substrate, and depositing a layer of nano film on the glass substrate to obtain a semi-finished product;
2) placing the semi-finished product obtained in the step 1) in a rapid annealing furnace under the air atmosphere condition, performing rapid annealing treatment at 500 ℃ for 1 hour, and naturally cooling to room temperature to obtain the rutile phase SnO 2 A film.
Examples of the experiments
The results of the tests conducted on the rutile phase tin dioxide films obtained in examples 1 and 2 and the comparative example are as follows.
FIG. 1 is a schematic representation of a composition comprising the rutile phase SnO obtained in examples 1, 2 and 3 2 X-ray diffraction pattern of the film. As can be seen from FIG. 1, the SnO obtained by the invention 2 The phase structure of the film is rutile phase tin dioxide, and no other impurities appear. This results in the tin dioxide film of the invention having good chemical stability and mechanical strength.
FIG. 3 shows rutile phase SnO of example 2 2 SEM spectra of the films at different magnifications. As can be seen from fig. 3, the surface of the film is very smooth, flat, uniform and dense.
FIG. 4 is example 2SnO 2 TEM high resolution spectra of the films. As can be seen from fig. 4, all the films had been crystallized, the crystallization property was good, and the rutile phase was formed.
FIG. 5 shows example 2 gold redLithofacies SnO 2 EDS spectrum of the film, with atomic ratio of tin to oxygen in the film of about 1: 2.
FIG. 6 shows rutile phase SnO of example 2 2 XPS spectra of Sn3d for the films. As can be seen from FIG. 6, SnO obtained in example 2 2 In the film, the valence of tin is positive quadrivalence, namely tin dioxide. The XPS spectrum shows that the tin has very good spectrum symmetry, and the tin exists in a high valence state.
FIG. 7 shows rutile phase SnO of example 2 2 XPS spectra of O1s for films. The O1s spectrum is subjected to peak separation to obtain two peaks, wherein the binding energies are respectively 530eV and 531.7eV, and the binding energies are respectively lattice oxygen and adsorbed oxygen.
The tin dioxide film is used for testing the hydrogen sensitivity, the response and recovery time, the sensitivity and other performances. The test system is a set of self-assembled instrument and mainly comprises four parts: (1) a terminal data acquisition system; the test signals were monitored using Keithley 2400 and the signals were collected and transmitted to a computer for processing. The software matched with the computer controls 2400, so that the current can be changed, the instrument starts and ends, data obtained by testing are drawn in real time, the final result is displayed, and the testing data is obtained. (2) A gas storage test chamber; the chamber used in the invention utilizes a modified high-temperature vacuum furnace, a pair of air inlet holes and air outlet holes are matched in the chamber, and the furnace can be used for pumping high vacuum and testing the gas-sensitive performance under the vacuum condition. (3) A gas flow controller; during the test hydrogen, in order to detect the accurate nature of sensor, can detect the hydrogen of different concentrations generally, just need the flowmeter to control this moment. Knowing the volume of the chamber in which the gas is stored, the detected gas concentration is obtained by controlling the gas flow rate and the gas release time. In addition, hydrogen is flammable and explosive, and the hydrogen concentration is greater than 4% and is easy to explode, so that the flowmeter can also effectively detect and avoid the hydrogen concentration from being too high and causing danger. (4) A gas source; the gas cylinder for loading gas is directly purchased from a manufacturer, and the instrument is matched with two gas cylinders: pure argon and hydrogen-argon mixed gas. The ratio of hydrogen to argon in the mixed gas is 1: 4.
FIG. 8 is the rutile phase SnO of example 2 2 Of filmsGas-sensitive spectrum. As can be seen from FIG. 8, SnO was introduced before hydrogen gas introduction 2 The resistance of the film is only 80.3 omega, and when SnO is reached 2 When hydrogen (100ppm) is introduced to the surface of the film, the film resistance is reduced to 68 omega, and when the introduction of the hydrogen is stopped, the film resistance is increased, so that good gas-sensitive performance is shown.
Comparative example 1
Deposited SnO of this comparative example 2 The preparation method of the film comprises the following steps:
1) cleaning the glass substrate: sequentially putting the glass substrate into acetone, isopropanol, ethanol and deionized water for ultrasonic cleaning, wherein the cleaning time is 20min each time, and the cleaning temperature is 50 ℃; taking out the substrate after ultrasonic cleaning, wiping the substrate clean by using a dust-free cloth, and finally putting the substrate into a sputtering cavity of a remote source plasma sputtering system for sputtering;
2) sputtering: the method takes argon as a plasma gas source, oxygen as a reaction gas, and adopts a remote source plasma sputtering technology to perform reactive sputtering deposition on a glass substrate to form a film, and specifically comprises the following steps:
before reactive sputtering, the sputtering chamber of the far-source plasma sputtering system is vacuumized to 2 x 10 -6 mbar, introducing argon of 80sccm into the cavity, and starting a plasma source emission system after the pressure in the cavity is kept stable so as to generate plasma at the plasma source; starting a plasma bunching electromagnet to enable the plasma to bombard the target material and pre-sputter the target material;
introducing oxygen into the chamber with a flow rate of 10sccm and a pressure of 4 × 10 in the sputtering chamber -3 mbar, wherein the used argon and oxygen are high-purity gases with the purity of not less than 99.999%; after the air pressure in the chamber and the voltage of the target material are stabilized, opening a baffle plate tightly attached to the lower part of the glass substrate, and starting to perform reactive sputtering deposition on the film;
in the reactive sputtering process, the power of a plasma emission source is 500W, the accelerating bias power of a target material is 100W, the sputtering speed is 20nm/min, the sputtering time is 20min, the sputtering temperature is 20 ℃, and the temperature of a glass substrate is normal temperature;
wherein the sputtering target is a tin target (the purity is 5N);
after the reactive sputtering is finished, closing the baffle below the glass substrate, and depositing a layer of nano film on the glass substrate, namely the deposition state SnO 2 A film.
The obtained SnO in a deposited state 2 The X-ray diffraction pattern of the film is shown in FIG. 4. As can be seen from the figure, the film is in an amorphous state. The film directly sputtered and deposited at normal temperature has no crystallization because SnO is not satisfied 2 The thermodynamic conditions for crystal formation are difficult to form crystal nuclei and grow up, and a stable crystal structure cannot be formed.
The result of the gas-sensitive experiment is shown in FIG. 9, where the sheet resistance is 820 Ω before introducing hydrogen gas at room temperature, and when SnO is exposed to oxygen 2 When hydrogen is introduced to the surface of the film, the resistance of the film is basically unchanged.
Comparative example 2
The comparative example prepares the tin dioxide film by a sol-gel method, and comprises the following steps:
(1) 1.13g of SnCl are taken 2 ·2H 2 Pouring O into a conical flask filled with 50mL of absolute ethanol to obtain 0.1mol/L SnO 2 And (3) solution.
(2) Stirring at room temperature for 3h, and standing for 24h to obtain colorless transparent colloidal solution.
(3) Drying with acetone, alcohol, deionized water, spin coating, drying at 100 deg.C for 10min, and repeating the above steps for 10 times to obtain gel with certain thickness.
(4) Putting the sample into a tubular heating furnace for sintering at 500 ℃, and naturally cooling after 2h to obtain SnO 2 And (4) a nano film.
The gas-sensitive experiment shows that the resistance is extremely high (more than 200k omega) at room temperature before hydrogen is introduced, and the film resistance is basically unchanged after the hydrogen is introduced.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. A preparation method of a tin dioxide oxide film is characterized in that tin is prepared into a deposited tin dioxide film by utilizing far-source plasma sputtering, and then a rutile phase tin dioxide film is obtained by annealing treatment;
the resistance of the tin dioxide oxide film is 80-100 omega before hydrogen is introduced at room temperature, and the resistance of the tin dioxide oxide film after the hydrogen is introduced is 50-70 omega;
in the sputtering of the far-source plasma, the pressure in a sputtering cavity is 2-5 multiplied by 10 < -3 > mbar; the sputtering speed is 10-50 nm/min, and the sputtering time is 10-20 min; the sputtering temperature is 20-50 ℃, and the temperature of the substrate is normal temperature.
2. The method for preparing a tin dioxide oxide thin film according to claim 1, wherein the resistance before the hydrogen gas is introduced is 80 to 85 Ω; the resistance after the hydrogen is introduced is 65-70 omega.
3. The method for preparing a tin dioxide oxide thin film according to claim 1, wherein the annealing temperature is 300 to 500 ℃.
4. The method according to claim 1, wherein the oxygen is a reactive gas and the flow rate of the oxygen is 1 to 10sccm in the remote plasma sputtering.
5. The method according to claim 1, wherein in the remote plasma sputtering, argon gas is used as a plasma gas source, and the flow rate of argon gas is 50 to 100 sccm.
6. The method of claim 1, wherein the power of the plasma emission source is 300-500W during the remote plasma sputtering.
7. The method according to claim 1, wherein the target accelerating bias power is 50-100W in the remote plasma sputtering.
8. The application of the tin dioxide oxide film obtained by the preparation method of any one of claims 1 to 7 in hydrogen detection.
9. A hydrogen gas sensor is characterized by comprising a gas sensitive element and a fixing frame, wherein the gas sensitive element is arranged on the fixing frame, and the gas sensitive element is a tin dioxide oxide film obtained by the preparation method of any one of claims 1 to 7.
10. A method for detecting hydrogen, characterized in that a tin dioxide oxide thin film obtained by the preparation method of any one of claims 1 to 7 is passed through a gas to be detected containing hydrogen, and a change in resistance of the tin dioxide oxide thin film is detected.
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CN105244406A (en) * 2015-10-23 2016-01-13 中国石油大学(华东) Ultraviolet detector based on palladium/tin dioxide/silicon heterojunction and preparation method thereof
CN105821378A (en) * 2016-05-20 2016-08-03 郑州大学 Niobium-doped tin dioxide transparent electric conducting film and preparation method thereof
CN111705306A (en) * 2020-07-21 2020-09-25 深圳扑浪创新科技有限公司 Zinc-doped tin oxide transparent conductive film and preparation method and application thereof

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US20190339227A1 (en) * 2018-05-03 2019-11-07 King Fahd University Of Petroleum And Minerals Room temperature hydrogen gas sensor

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Publication number Priority date Publication date Assignee Title
CN105244406A (en) * 2015-10-23 2016-01-13 中国石油大学(华东) Ultraviolet detector based on palladium/tin dioxide/silicon heterojunction and preparation method thereof
CN105821378A (en) * 2016-05-20 2016-08-03 郑州大学 Niobium-doped tin dioxide transparent electric conducting film and preparation method thereof
CN111705306A (en) * 2020-07-21 2020-09-25 深圳扑浪创新科技有限公司 Zinc-doped tin oxide transparent conductive film and preparation method and application thereof

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