CN110498440A - A kind of zinc oxide air-sensitive membrane material, preparation method and applications - Google Patents
A kind of zinc oxide air-sensitive membrane material, preparation method and applications Download PDFInfo
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- CN110498440A CN110498440A CN201910623385.XA CN201910623385A CN110498440A CN 110498440 A CN110498440 A CN 110498440A CN 201910623385 A CN201910623385 A CN 201910623385A CN 110498440 A CN110498440 A CN 110498440A
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- zinc oxide
- membrane material
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- sensitive membrane
- air
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
It is directly to prepare nanostructured zinc oxide film using solution low-temperature in-site deposition on the electrode substrate the invention discloses a kind of zinc oxide air-sensitive membrane material, preparation method and applications.There is prepared nanostructured zinc oxide film the nanometer sheet of vertical substrate growth to be formed by network-like structure.The present invention has the advantages that efficient, low in cost, simple process, is suitable for industrialized production.Gained nanostructured zinc oxide film has biggish specific surface area, the agglomeration traits between nano particle can be effectively overcome, to NO2、H2The gases such as S are responded with good air-sensitive, have fabulous air-sensitive application prospect.
Description
Technical field
The present invention relates to metal oxide film field of material preparation, and in particular to a kind of zinc oxide air-sensitive membrane material, preparation
Method and its application.
Background technique
With the development and the improvement of people's living standards of social economy, the environment that people live to oneself, especially
Air quality proposes more and more requirements, and inflammable to indoor and outdoor low concentration, explosive and toxic gas detection is also increasingly
Pay attention to.Gas sensor is a kind of sensor for detecting specific gas.It is utilized is occurred between under test gas and sensitive material
Physical-chemical reaction, be that electrical signal form exports by the concentration of under test gas and conversion, according to the variation of electric signal from
And confirm gas componant and concentration.Itself resistance value when resistance-type gas sensor is contacted using semiconductor material and gas
Variation is to detect specific gas, and sensitive material used is based on metal oxide, such as SnO2、ZnO、WO3Deng with production method
Simply, high sensitivity, detection limit it is low, long service life, it is at low cost the advantages that.
Zinc oxide is a kind of typical n-type semiconductor, forbidden bandwidth 3.2eV.Air-sensitive zinc oxide material is mostly nanometer
Powder, as CN201510150594.9 discloses a kind of preparation method of loose acicular type zinc oxide gas sensor；
CN201710451594.1 discloses a kind of flake porous zinc oxide gas sensitive of two-dimensional square and preparation method thereof；
CN201210124133.0 discloses a kind of preparation method of pectination nanostructured zinc oxide gas sensor.Since air-sensitive measures
Gas sensitive need to be deposited on to electrode surface film forming, therefore the typical process of nano-powder production gas sensitive device is by nano-powder
It is scattered in organic bond and forms slurry, then by slurry coating or be printed on electrode base sheet, removed finally by heat treatment
Organic bond is removed, to obtain air-sensitive membrane material.It can be seen that being related to from nano-powder to air-sensitive membrane material is made on the electrode
And to the secondary operation to powder, the processes such as grinding in slurry manufacturing process may destroy nanostructure, and apply institute
The membrane material obtained is generally thicker (being greater than 10 microns), and the nano particle of a large amount of deep layers coatings fails to play one's part to the full.Document
(Sensors and Actuators B 173 (2012) 897-902) reports a kind of in-situ deposition of ZnO nano chip arrays film
Method, preparation method use the solvent-thermal method using dehydrated alcohol as solvent, and reaction temperature is 95 DEG C.Document (Sensors and
Actuators B 195 (2014) 71-79) a kind of ZnO nano chip arrays film prepared using chemical vapor deposition is reported, it steams
It rises for zinc chloride and inidum chloride, film deposition temperature is 450 DEG C.Document (Sensors and Actuators B 221
(2015) 350-356) a kind of ZnO nano chip arrays film of hydro-thermal method preparation is reported, hydrothermal temperature is 95 DEG C.Document
(Sensors and Actuators B 204 (2014) 96-101) is reported a kind of to be prepared under 80 DEG C of bath temperature
ZnO nano chip arrays film.
Above-mentioned preparation method reaction system is complicated, and solution system is complicated, and temperature is high, and not easy to operate and energy consumption is big.
Summary of the invention
Based on the prior art, the present invention provides a kind of zinc-oxide nano membrane material, cryogenic fluid in-situ deposition method, can
It completes at room temperature, film growth rates are fast, and solution system is simple.The zinc-oxide nano membrane material is additionally provided simultaneously
Purposes.
The object of the invention is realized by following proposal:
A kind of preparation method of zinc oxide air-sensitive membrane material, which is characterized in that using chemical baths directly in electrode base sheet
Upper low temperature depositing nanostructured zinc oxide film, specifically comprises the following steps:
(1) ZnO seed crystal film is prepared on the ceramic substrate for be printed on electrode；
(2) configuration of zinc oxide precursor liquid solution: being dissolved in distilled water for zinc salt and alkali respectively, and above-mentioned solution is mixed, is stirred
It mixes, zinc oxide precursor liquid solution is made；
(3) ceramic substrate for being covered with ZnO seed crystal film the solution in-situ deposition of nanostructured zinc oxide film: is immersed in oxygen
Change in zinc precursor solution, solution is placed in 0~25 DEG C of progress film deposition, sedimentation time is 0.1~10 hour, and deposition terminates
After take out ceramic substrate, cleaning is dried.
Further, the ZnO seed crystal film passes through sol-gal process, thermal evaporation or sputtering method preparation.
Further, the zinc salt is Zn (NO3)2、Zn(CH3COO)2、ZnSO4、ZnCl2One of.
Further, one of alkali NaOH, KOH, ammonium hydroxide.
Further, the molar ratio of zinc salt and alkali is 0.1~0.3.
The zinc oxide air-sensitive membrane material of the preparation method preparation, it is characterised in that: by the zinc oxide nano of nano-scale
Rice piece composition, the vertical substrate of Zinc oxide nano sheet and cross arrangement composition network-like structure.
The zinc oxide air-sensitive membrane material, for detecting NO2、H2S gas.
A kind of gas sensor made of the zinc oxide air-sensitive membrane material.
The preparation method of zinc oxide air-sensitive membrane material of the present invention, directly on the electrode substrate using solution in-situ deposition
Growing zinc oxide with nanometer structure film prepares ZnO seed crystal film on the electrode substrate first, provides nanostructured zinc oxide film
Growth in situ nucleus.Used zinc oxide precursor liquid solution is formulated by zinc salt and alkali, containing only zinc salt and alkali, solution system
Simply.Dip the substrate into zinc oxide precursor liquid solution, by room temperature can growth in situ nanostructured zinc oxide it is thin
Film, and film growth rates are fast；Have the advantages that efficient, low in cost, simple process, is suitable for industrialized production.
Gained nanostructured zinc oxide film has biggish specific surface area, can effectively overcome the reunion between nano particle
Problem, to H2The gases such as S are responded with good air-sensitive.Cryogenic fluid growth in situ nanostructured zinc oxide film repeatability
It is good, using its preparation gas sensor high yield rate, it can be achieved that the low temperature of object gas, efficiently, quickly detection.
Detailed description of the invention
Fig. 1 is the scanning electron microscope diagram of nanostructured zinc oxide film prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram of nanostructured zinc oxide film prepared by embodiment 2.
Fig. 3 is the nanostructured zinc oxide air-sensitive film of the preparation of embodiment 2 at room temperature to various concentration NO2Gas moves
State response curve.
Fig. 4 is the scanning electron microscope diagram of nanostructured zinc oxide film prepared by embodiment 3.
Fig. 5 be embodiment 3 prepare nanostructured zinc oxide air-sensitive film at 70 DEG C to various concentration H2The dynamic of S gas
Response curve.
Specific embodiment
The following examples are not intended to limit the scope of the invention to further explanation of the invention.
The preparation method of zinc oxide air-sensitive membrane material of the present invention prepares ZnO seed crystal film on the electrode substrate first, mentions
For the growth in situ nucleus of nanostructured zinc oxide film.ZnO seed crystal film can pass through the side such as sol-gal process, thermal evaporation, sputtering
Method preparation.
Then, zinc oxide precursor liquid solution is prepared by zinc salt and alkali, the molar ratio of zinc salt and alkali is 0.1~0.3.Zinc salt is
Zn(NO3)2、Zn(CH3COO)2、ZnSO4、ZnCl2One of；Alkali is one of NaOH, KOH, ammonium hydroxide.
It dips the substrate into zinc oxide precursor liquid solution, solution is placed in 0~25 DEG C and keeps the temperature 0.1~10 hour, is taken out
Ceramic substrate, cleaning are dried.It at room temperature can growth in situ nanostructured zinc oxide film.
Embodiment 1:
(1) 1:0.1 weighs a certain amount of KOH and Zn (NO in molar ratio3)2, it is dissolved in distilled water respectively；By above-mentioned solution
Mixing, stirring, are made zinc oxide precursor liquid solution；
(2) ceramic substrate for being covered with zinc oxide seed crystal film is immersed in zinc oxide precursor liquid solution, in 25 DEG C of water-bath
It is middle to stand 2 hours；
(3) ceramic substrate is taken out after standing, cleaning is dried.
Product prepared by the embodiment is put into scanning electron microscope and is observed, as shown in Figure 1, prepared nano zine oxide is thin
Film is made of the nanometer sheet of thickness about 20nm, and the vertical substrate growth of nanometer sheet forms network-like structure.
Embodiment 2:
(1) 1:0.2 weighs a certain amount of NaOH and ZnSO in molar ratio4, it is dissolved in distilled water respectively；Above-mentioned solution is mixed
It closes, stirring, zinc oxide precursor liquid solution is made；
(2) ceramic substrate for being covered with zinc oxide seed crystal film is immersed in zinc oxide precursor liquid solution, in 10 DEG C of water-bath
It is middle to stand 5 hours；
(3) ceramic substrate is taken out after standing, cleaning is dried.
As shown in Fig. 2, prepared Nano zinc oxide film is made of the nanometer sheet of thickness about 30nm, the vertical substrate of nanometer sheet
Growth forms network-like structure.
Fig. 3 is the Nano zinc oxide film of the preparation of embodiment 3 at room temperature to various concentration NO2The dynamic response of gas is bent
Line, it is seen that it is to NO2Gas detection concentration can be down to 40ppb, to 1ppm NO2The response sensitivity of gas is 78.
Embodiment 3:
(1) 1:0.3 takes a certain amount of ammonium hydroxide and ZnCl in molar ratio2, it is dissolved in distilled water respectively；Above-mentioned solution is mixed
It closes, stirring, zinc oxide precursor liquid solution is made；
(2) ceramic substrate for being covered with zinc oxide seed crystal film is immersed in zinc oxide precursor liquid solution, in 0 DEG C of water-bath
Stand 10 hours；
(3) ceramic substrate is taken out after standing, cleaning is dried.
As shown in figure 4, prepared Nano zinc oxide film is made of the nanometer sheet of thickness about 50nm, the vertical substrate of nanometer sheet
Growth forms network-like structure.
Fig. 5 be embodiment 3 prepare Nano zinc oxide film at 70 DEG C to various concentration H2The dynamic response of S gas is bent
Line, it is seen that its H to 5~50ppm2Good air-sensitive response is presented in S gas, to the H of 50ppm2The response sensitivity of S gas is
48。
The embodiment is a preferred embodiment of the present invention, but present invention is not limited to the embodiments described above, not
In the case where substantive content of the invention, any conspicuous improvement that those skilled in the art can make, replacement
Or modification all belongs to the scope of protection of the present invention.
Claims (8)
1. a kind of preparation method of zinc oxide air-sensitive membrane material, which is characterized in that be directly printed on electrode using chemical baths
Low temperature depositing nanostructured zinc oxide film, specifically comprises the following steps: on ceramic substrate
(1) ZnO seed crystal film is prepared in the ceramic substrate for being printed on electrode；
(2) configuration of zinc oxide precursor liquid solution: being dissolved in distilled water for zinc salt and alkali respectively, above-mentioned solution is mixed, stirring, system
Obtain zinc oxide precursor liquid solution；
(3) ceramic substrate for being covered with ZnO seed crystal film the solution in-situ deposition of nanostructured zinc oxide film: is immersed in zinc oxide
In precursor solution, solution is placed in 0~25 DEG C of progress film deposition, sedimentation time is 0.1~10 hour, is taken after deposition
Ceramic substrate out, cleaning are dried.
2. the preparation method of zinc oxide air-sensitive membrane material according to claim 1, it is characterised in that: the ZnO seed crystal film
It is prepared by sol-gal process, thermal evaporation or sputtering method.
3. the preparation method of zinc oxide air-sensitive membrane material according to claim 1, it is characterised in that: the zinc salt is Zn
(NO3)2、Zn(CH3COO)2、ZnSO4、ZnCl2One of.
4. the preparation method of zinc oxide air-sensitive membrane material according to claim 1, it is characterised in that: alkali NaOH, KOH,
One of ammonium hydroxide.
5. the preparation method of zinc oxide air-sensitive membrane material according to claim 1, it is characterised in that: mole of zinc salt and alkali
Than being 0.1~0.3.
6. the zinc oxide air-sensitive membrane material of the described in any item preparation method preparations of claim 1-5, it is characterised in that: by nanometer
The Zinc oxide nano sheet of size forms, the vertical substrate of Zinc oxide nano sheet and cross arrangement composition network-like structure.
7. zinc oxide air-sensitive membrane material as claimed in claim 6, for detecting NO2、H2S gas.
8. a kind of gas sensor made of zinc oxide air-sensitive membrane material as claimed in claim 6.
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| CN112683961A (en) * | 2020-12-02 | 2021-04-20 | 赛莱克斯微系统科技（北京）有限公司 | Gas sensor and method for manufacturing gas-sensitive film thereof |
| CN113308680A (en) * | 2021-04-16 | 2021-08-27 | 沈阳化工大学 | Preparation method and application of ZnO nanowire sensitive material |
| CN115595565A (en) * | 2022-10-26 | 2023-01-13 | 山东胜利通海集团东营天蓝节能科技有限公司（Cn） | Preparation method and application of complex-phase ZnO/ZnS nano array film |
| CN116177590A (en) * | 2023-03-23 | 2023-05-30 | 河南科技大学 | Preparation method of ZnO micro-nano structural material constructed by cross growth of nano sheets |
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| CN115595565A (en) * | 2022-10-26 | 2023-01-13 | 山东胜利通海集团东营天蓝节能科技有限公司（Cn） | Preparation method and application of complex-phase ZnO/ZnS nano array film |
| CN116177590A (en) * | 2023-03-23 | 2023-05-30 | 河南科技大学 | Preparation method of ZnO micro-nano structural material constructed by cross growth of nano sheets |
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