CN102662002A - Semi-conductor film, gas sensor and preparation method thereof - Google Patents
Semi-conductor film, gas sensor and preparation method thereof Download PDFInfo
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- CN102662002A CN102662002A CN2012101248429A CN201210124842A CN102662002A CN 102662002 A CN102662002 A CN 102662002A CN 2012101248429 A CN2012101248429 A CN 2012101248429A CN 201210124842 A CN201210124842 A CN 201210124842A CN 102662002 A CN102662002 A CN 102662002A
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- metal oxide
- polymkeric substance
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- oxide semiconductor
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Abstract
The invention relates to a preparation method of a semi-conductor film, which comprises the following steps that: solvent is used for preparing the mixed solution of semiconductor metal oxide and polymer; the mixed solution is covered in a sensitive film area of a sensor device; and the sensor device is vacuumized and dried, so that the semi-conductor film is formed in the sensitive film area of the sensor device. Correspondingly, the invention also provides the semi-conductor film and a sensor with the film as a sensitive film. The sensor can detect gas at room temperature, has short response and recovery time, good selectivity and a simple manufacturing method, is easy to operate, is low in cost and is applicable to mass production.
Description
Technical field
The present invention relates to sensor technical field, particularly a kind of semiconductive thin film, gas sensor and preparation method thereof.
Background technology
Surface acoustic wave (SAW) gas sensor is widely used in fields such as environmental monitoring, chemical treatment control and clinical analysiss, can be to SO
2, water vapour, acetone, methyl alcohol, H
2, H
2S, NO
2Detect etc. multiple gases.Sonic surface wave gas sensors is made up of SAW device and sensitive membrane.The former is meant on piezoelectric substrate and makes interdigital transducer (IDT) and formation energy conversion apparatus in pairs.The latter be meant with special process on the transmission channel of SAW device sound wave, cover to the selective adsorbing thin film of gas to be measured.Through detecting the change that occurs the indexs such as phase place, frequency and delay of output AC electric signal on the output IDT, just can reflect the absorption of sensitive membrane, and then can infer the amount and the concentration of gas to be measured gas to be measured.
Most of existing sonic surface wave gas sensors uses metal oxide semiconductor to do sensitive thin film separately.Though metal oxide semiconductor film resistance rate is big, susceptibility is high, and its working temperature is high.High temperature not only influences the sensor stablizing effect, also can bring the problem of excess power loss.And the metal oxide semiconductor film is at room temperature a little less than the adsorptive power to most gases, causes the variation of density, elasticity coefficient and resistivity of semiconductive thin film all very little, and then also very faint to the influence of surface acoustic wave.Also have some sonic surface wave gas sensors to use polymer film to do sensitive thin film separately.Though at normal temperatures gas is had very strong adsorbability, its susceptibility is little, and change in resistance is faint, therefore needs very long response and release time.
In addition, the method for existing making sensitive thin film, like sol-gel process, magnetron sputtering method, in-situ chemical oxidative polymerization method, CVD etc., these manufacture crafts are comparatively complicated, and production cost is higher.
Therefore, when reducing cost, produce can carry out at normal temperatures fast, the gas sensor of Sensitive Detection seems particular importance, also the sensitive membrane to sensor has proposed requirements at the higher level.
Summary of the invention
To shortcomings such as above-mentioned gas sensor temperature height, response recovery time length, sensitive membrane complex manufacturing technology; The purpose of this invention is to provide semiconductive thin film that is used for gas sensor and the gas sensor that comprises this semiconductive thin film, can quick, sensitive at normal temperatures detected gas.Gas sensor that the present invention also aims to the simple semiconductive thin film of manufacture craft to be provided and to comprise this semiconductive thin film and corresponding manufacturing process.
The present invention provides a kind of method for making of semiconductive thin film, and this method may further comprise the steps:
A) mixed solution of use solvent configuring semiconductor metal oxide and polymkeric substance;
B) make mixed solution cover the sensitive membrane zone of sensor component;
C), thereby form semiconductive thin film in sensor component sensitive membrane zone with the sensor component vacuum drying.
In addition, the present invention provides a kind of semiconductive thin film, is formed on the sensor sensing diaphragm area, it is characterized in that, this film comprises metal oxide semiconductor and two kinds of materials of polymkeric substance at least.
Moreover the present invention provides a kind of sensor, is coated with sensitive membrane in its sensitive membrane zone, it is characterized in that, the sensitive membrane of said sensor comprises metal oxide semiconductor and two kinds of materials of polymkeric substance at least.
Compared with prior art, adopt technical scheme provided by the invention to have the following advantages: to compare with the pure semiconductor metal oxide film, use the composite membrane that comprises metal oxide semiconductor and polymkeric substance, at room temperature detected gas; Compare with the straight polymer film, as long as the response of above-mentioned composite membrane and release time are tens seconds; In addition, the selectivity of this composite membrane detected gas is very good, and method for making is simple, and is easy to operate, and low cost is fit to produce in enormous quantities.
Description of drawings
Through reading the detailed description of doing with reference to following accompanying drawing that non-limiting example is done, it is more obvious that other features, objects and advantages of the present invention will become:
Fig. 1 is the process flow diagram according to semiconductive thin film method for making of the present invention;
Fig. 2 (a) and Fig. 2 (b) are the cross-sectional view in each stage of the sensor of sensitive membrane for making with above-mentioned semiconductive thin film according to flow process shown in Figure 1 according to the present invention.
Embodiment
Describe embodiments of the invention below in detail, the example of said embodiment is shown in the drawings.Be exemplary through the embodiment that is described with reference to the drawings below, only be used to explain the present invention, and can not be interpreted as limitation of the present invention.
Disclosing of hereinafter provides many various embodiment or example to be used for realizing different structure of the present invention.Of the present invention open in order to simplify, hereinafter the parts and the setting of specific examples are described.Certainly, they only are example, and purpose does not lie in restriction the present invention.In addition, the present invention can be in different examples repeat reference numerals and/or letter.This repetition is in order to simplify and purpose clearly, itself not indicate the relation between various embodiment that discuss of institute and/or the setting.In addition, the invention provides various specific technologies and examples of material, but those skilled in the art can recognize the property of can be applicable to of other technologies and/or the use of other materials.Should be noted that the not necessarily drafting in proportion of illustrated in the accompanying drawings parts.The present invention has omitted description to known assemblies and treatment technology and technology to avoid unnecessarily limiting the present invention.
Below, the method that forms semiconductive thin film among Fig. 1 is carried out concrete description.
Execution in step S101, the mixed solution of use solvent configuring semiconductor metal oxide and polymkeric substance.Metal oxide semiconductor can be SnO
2, ZnO, WO
3, CuO-ZnO, CuO-SnO
2, Fe
2O
3-ZnO, Al
2O
3A kind of or its combination among-the ZnO.Polymkeric substance can be a kind of or its combination in polyaniline (PANI), polypyrrole (PPY), polyisobutylene (PIB), the polythiophene.In one embodiment of the invention, metal oxide semiconductor is SnO
2, polymkeric substance is a polyaniline.In one embodiment of the invention, said solvent is a nitrogen nitrogen dimethylformamide.The mass ratio of metal oxide semiconductor and polymkeric substance and solvent can be for example 1: 2: 5.With above-mentioned mixed solution sonic oscillation, its purpose is to make metal oxide semiconductor and polymkeric substance in solvent, fully to disperse.Typically, ultrasonic temperature can be 60 ℃, and ultrasonic time can be 1 to 2 hours.
Execution in step S102 makes mixed solution cover the sensitive membrane zone of sensor component.In one embodiment of the invention, be coated with above-mentioned mixed solution regional the dripping of the sensitive membrane of sensor component.Typically, drip applying mixed solution dosage can for a few μ l to tens μ l.Compare film techniques such as sol-gel process, magnetron sputtering method, in-situ chemical oxidative polymerization method, CVD, a coating method is simpler, easy to operate, and low cost is fit to produce in enormous quantities.
Execution in step S103 with the sensor component vacuum drying, thereby forms semiconductive thin film in sensor component sensitive membrane zone.Its purpose is to remove moisture and the organism in the sensitive membrane.Typically, the vacuum drying temperature can be 140 ℃, and the vacuum drying time can be at least 2 hours.
Down in the face of describing according to the formed semiconductive thin film of the method for making of above-mentioned semiconductive thin film.
Said film comprises metal oxide semiconductor and two kinds of materials of polymkeric substance at least.Wherein, the mass ratio of metal oxide semiconductor and polymkeric substance can be for example 1: 2.In one embodiment of the invention, metal oxide semiconductor is SnO
2, polymkeric substance is a polyaniline.Typically, the thickness range of semiconductive thin film can be 500nm-2um.
Below according to Fig. 2 (a) and Fig. 2 (b) to being that the sensor of sensitive membrane describes with above-mentioned semiconductive thin film.
With reference to figure 2 (a) and Fig. 2 (b), the sensor comprises quartz substrate 100, interdigital transducer 220 and sensitive membrane 310.Wherein, sensitive membrane 310 is formed on the sensitive membrane zone 210 of piezoelectric substrate.Sensitive membrane 310 comprises metal oxide semiconductor and two kinds of materials of polymkeric substance at least.Wherein, the mass ratio of metal oxide semiconductor and polymkeric substance can be for example 1: 2.In one embodiment of the invention, metal oxide semiconductor is SnO
2, polymkeric substance is a polyaniline, said sensor can be used for detecting NO gas.Typically, the thickness range of sensitive membrane can be 500nm-2um.
Though specify about example embodiment and advantage thereof, be to be understood that under the situation of the protection domain that does not break away from the qualification of spirit of the present invention and accompanying claims, can carry out various variations, replacement and modification to these embodiment.For other examples, when those of ordinary skill in the art should understand easily in keeping protection domain of the present invention, the order of processing step can change.
In addition, range of application of the present invention is not limited to technology, mechanism, manufacturing, material composition, means, method and the step of the specific embodiment of describing in the instructions.From disclosure of the present invention; To easily understand as those of ordinary skill in the art; For the technology, mechanism, manufacturing, material composition, means, method or the step that have existed or be about to later on develop at present; Wherein they are carried out the corresponding embodiment cardinal principle identical functions of describing with the present invention or obtain identical substantially result, can use them according to the present invention.Therefore, accompanying claims of the present invention is intended to these technology, mechanism, manufacturing, material composition, means, method or step are included in its protection domain.
Claims (21)
1. the method for making of a semiconductive thin film, this method may further comprise the steps:
A) mixed solution of use solvent configuring semiconductor metal oxide and polymkeric substance;
B) make mixed solution cover the sensitive membrane zone of sensor component;
C), thereby form semiconductive thin film in sensor component sensitive membrane zone with the sensor component vacuum drying.
2. method according to claim 1, wherein, in said step a):
The mass ratio of metal oxide semiconductor and polymkeric substance and solvent is 1: 2: 5.
3. method according to claim 1, wherein, in said step a):
Metal oxide semiconductor comprises SnO
2, ZnO, WO
3, CuO-ZnO, CuO-SnO
2, Fe
2O
3-ZnO, Al
2O
3A kind of or its combination among-the ZnO.
4. according to claim 1 or 3 described methods, wherein, in said step a):
Polymkeric substance comprises a kind of or its combination in polyaniline, polypyrrole, polyisobutylene, the polythiophene.
5. method according to claim 1, wherein, in said step a):
Metal oxide semiconductor is SnO
2, polymkeric substance is a polyaniline.
6. method according to claim 1, wherein, said solvent comprises nitrogen nitrogen dimethylformamide.
7. method according to claim 1, wherein, said step a) also comprises:
Said mixed solution is used supersonic oscillations.
8. method according to claim 1, wherein, said step b) comprises:
Said mixed solution dripped be coated in sensor component sensitive membrane zone.
9. a semiconductive thin film is formed on the sensor sensing diaphragm area, it is characterized in that, said film comprises metal oxide semiconductor and two kinds of materials of polymkeric substance at least.
10. film according to claim 9, wherein, the mass ratio of metal oxide semiconductor and polymkeric substance is 1: 2.
11. film according to claim 9, wherein, metal oxide semiconductor comprises SnO
2, ZnO, WO
3, CuO-ZnO, CuO-SnO
2, Fe
2O
3-ZnO, Al
2O
3A kind of or its combination among-the ZnO.
12. according to claim 9 or 11 described films, wherein, polymkeric substance comprises a kind of or its combination in polyaniline, polypyrrole, polyisobutylene, the polythiophene.
13. film according to claim 9, wherein, metal oxide semiconductor is SnO
2, polymkeric substance is a polyaniline.
14. film according to claim 9, its thickness range are 500nm-2um.
15. a sensor is coated with sensitive membrane in its sensitive membrane zone, it is characterized in that, the sensitive membrane of said sensor comprises metal oxide semiconductor and two kinds of materials of polymkeric substance at least.
16. sensor according to claim 15 is characterized in that, said sensor also comprises substrate and slotting finger transducer.
17. sensor according to claim 15, wherein, the mass ratio of metal oxide semiconductor and polymkeric substance is 1: 2.
18. sensor according to claim 15, wherein, metal oxide semiconductor comprises SnO
2, ZnO, WO
3, CuO-ZnO, CuO-SnO
2, Fe
2O
3-ZnO, Al
2O
3A kind of or its combination among-the ZnO.
19. according to claim 15 or 18 described sensors, wherein, polymkeric substance comprises a kind of or its combination in polyaniline, polypyrrole, polyisobutylene, the polythiophene.
20. sensor according to claim 15, wherein, metal oxide semiconductor is SnO
2, polymkeric substance is a polyaniline.
21. sensor according to claim 15, wherein, the sensitive membrane thickness range is 500nm-2um.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105092658A (en) * | 2015-08-18 | 2015-11-25 | 浙江大学 | Polyaniline/zinc oxide nano composite resistor type material sensor and preparation method thereof |
| CN105136869A (en) * | 2015-08-18 | 2015-12-09 | 浙江大学 | Polyaniline/iron oxide nano composite resistance-type material sensor, and preparation method thereof |
| CN105651835A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Methanol gas sensor and preparation method thereof |
| CN106546635A (en) * | 2016-10-27 | 2017-03-29 | 扬州大学 | Preparation method based on p n abnormal shape heterojunction semiconductor nitrogen dioxide gas sensing layers |
| CN114235950A (en) * | 2021-11-19 | 2022-03-25 | 华南理工大学 | Method for reducing working temperature of semiconductor sensitive film in surface acoustic wave gas sensor |
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| JPWO2009148134A1 (en) * | 2008-06-04 | 2011-11-04 | 旭化成エレクトロニクス株式会社 | Quantum type infrared sensor and quantum type infrared gas concentration meter using the same |
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| CN102375029A (en) * | 2010-08-06 | 2012-03-14 | 中国科学院微电子研究所 | Method for making high selectivity semiconductor film material |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105651835A (en) * | 2014-11-12 | 2016-06-08 | 长沙理工大学 | Methanol gas sensor and preparation method thereof |
| CN105092658A (en) * | 2015-08-18 | 2015-11-25 | 浙江大学 | Polyaniline/zinc oxide nano composite resistor type material sensor and preparation method thereof |
| CN105136869A (en) * | 2015-08-18 | 2015-12-09 | 浙江大学 | Polyaniline/iron oxide nano composite resistance-type material sensor, and preparation method thereof |
| CN105136869B (en) * | 2015-08-18 | 2018-04-03 | 浙江大学 | Polyaniline/ferric oxide nano composite resistance type material sensors and preparation method thereof |
| CN106546635A (en) * | 2016-10-27 | 2017-03-29 | 扬州大学 | Preparation method based on p n abnormal shape heterojunction semiconductor nitrogen dioxide gas sensing layers |
| CN114235950A (en) * | 2021-11-19 | 2022-03-25 | 华南理工大学 | Method for reducing working temperature of semiconductor sensitive film in surface acoustic wave gas sensor |
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Application publication date: 20120912 |