CN101158662A - Thin film material used for hydrogen gas sensor and preparation method thereof - Google Patents

Thin film material used for hydrogen gas sensor and preparation method thereof Download PDF

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Publication number
CN101158662A
CN101158662A CNA2007100312431A CN200710031243A CN101158662A CN 101158662 A CN101158662 A CN 101158662A CN A2007100312431 A CNA2007100312431 A CN A2007100312431A CN 200710031243 A CN200710031243 A CN 200710031243A CN 101158662 A CN101158662 A CN 101158662A
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film material
thin film
alloy
gas sensor
hydrogen gas
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CNA2007100312431A
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欧阳柳章
秦发祥
朱敏
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South China University of Technology SCUT
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South China University of Technology SCUT
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Abstract

The invention discloses a hydrogen sensor thin film materials, which comprises substrates, an alloy thin film material and a protective thin film. The substrates and the protective thin film clamp are covered by the alloy firm material. Also the invention discloses a hydrogen sensor thin film materials preparation method. The alloy thin film material comprises a submicron or a nanometer crystal. The alloy thin film has the advantages of duplicate using, quick response speed, high sensitivity, broad measuring range, no frequent examination. The thin film material can be prepared into a portable solid hydrogen sensor, which has the advantages of low consumption, wide practical range, no environment constraint, wide hydrogen concentration measurement range, small size (about 100nm), high hydrogen sensitivity, and good sensitivity.

Description

Thin film material used for hydrogen gas sensor and preparation method thereof
Technical field
The present invention relates to the film of hydrogen gas sensor, particularly a kind of thin film material used for hydrogen gas sensor and preparation method thereof.
Background technology
Hydrogen is widely used in preparation and the process and the field of aerospace of semiconductive thin film, because the inflammability and the explosion hazard (explosion limits is 4～74%) of hydrogen make that the detection technique of hydrogen is quite important, so the design of hydrogen gas sensor also just seems particularly important with making, require hydrogen gas sensor can be reusable, response speed is fast, measurement range is wide, practical face width, need not often check, energy consumption is low.
Hydrogen gas sensor mainly contains two classes at present: a class is (as Ni by the 8th subgroup element, Pd, Pt etc.) block sensor of Zu Chenging, make hydrogen generation oxidation reaction detect the existence of hydrogen by heating and catalysis, but in testing process, oxidizable material is (as alcohol, carbohydrates such as acetone) be easy at Ni, Pd, react on the catalyst such as Pt, cause wrong report, yet alcohol, carbohydrates such as acetone often use in the semiconductor material process again, therefore exist the easy oxidizing gas of this class more or less in the site environment, brought inconvenience to detection; Another kind of sensor as metal one nonconductor semiconductor (MIS) or metal monooxide semiconductor (MOS) electric capacity, field effect transistor and Pd gate diode, but can only be used for detecting low-concentration hydrogen usually.
Summary of the invention
The present invention is in order to overcome the deficiency that above prior art exists, provide a kind of reusable, response speed is fast, measurement range is wide, practical face width, the thin film material used for hydrogen gas sensor that need not often check.
Another object of the present invention is to provide a kind of preparation method of thin film material used for hydrogen gas sensor.
Purpose of the present invention realizes by following technical scheme: this thin film material used for hydrogen gas sensor is characterized in that: described membraneous material comprises substrate, alloy film material and protective film; Substrate and protective film folder are covering alloy film material; The basis of alloy film material is Mg and Ni, and chemical composition is Mg [p-x]α [x]Ni [1-y]β [y], wherein α is Al, Mn, Sn, Ca, Li, B, La, Ce, Nd, Pr, Y or mishmetal, wherein β is Cu, Ti, Co, Fe, Cr, Zr, V, Nb, Mo or W, wherein 2≤p≤70,0≤x≤35,0≤y≤0.8.
Described substrate is metal, semiconductor or insulator substrate.
Described protective film is Pd, Pt or Au film, the perhaps binary of Pd, Pt, Ag, Au, Co or complex alloy thin film.
Described alloy film material thickness is 10～2000nm.
Described protective film thickness is 2～1000nm.
The preparation method of above-mentioned thin film material used for hydrogen gas sensor; it is characterized in that: at first with induction melting or powder metallurgy process prealloy target; use physical gas-phase deposite method then, on substrate, make alloy film material, then at alloy film material surface coverage one deck protective film.
Described physical gas-phase deposite method is sputter, electron beam evaporation plating or laser ablation method.
The basis of described alloys target is Mg and Ni, and chemical composition is Mg [p-x]α [x]Ni [1-y]β [y], wherein α is Al, Mn, Sn, Ca, Li, B, La, Ce, Nd, Pr, Y or mishmetal, wherein β is Cu, Ti, Co, Fe, Cr, Zr, V, Nb, Mo or W, wherein 2≤p≤70,0≤x≤35,0≤y≤0.8.
Described alloys target is the potpourri of two kinds or two or more described chemical compositions.
With the induction melting method reguline metal is smelted into alloy-steel casting, behind the high annealing, alloy-steel casting is processed into alloys target with wire cutting method; Perhaps with powder metallurgy process with metal powder sintered, behind the high annealing, be processed into alloys target with wire cutting method.
The application of this thin film material used for hydrogen gas sensor: this membraneous material, add that signal detection system just made hydrogen gas sensor, hydrogen gas sensor and hydrogen react, the composition and the structure of membraneous material change before and after the reaction, cause the physics of membraneous material and the change of chemical characteristic, the for example light transmission of membraneous material, reflective, electric conductivity, thermal effect, resistivity, electric capacity or magnetic resistance etc., the change of these performances can be used for detecting the concentration of hydrogen.Alloy film material surface coverage one deck hydrogen can freely pass through but not the then intransitable protective film of protium, reacts and reduces the detection sensitivity of hydrogen gas sensor to hydrogen to prevent alloy film material and harmful gas.Alloy film material is deposited on can be by light transmission that detects membraneous material or the concentration that reflective detects hydrogen on the glass substrate; Be deposited on the concentration that can detect hydrogen on semiconductor or the insulator substrate by the resistivity that detects membraneous material; Be deposited on the concentration that can detect hydrogen on the metal substrate by thermal effect, electric conductivity, electric capacity or the magnetic resistance that detects membraneous material.
The present invention has following advantage with respect to prior art: this thin film material used for hydrogen gas sensor, alloy film material wherein is by sub-micron or nanocrystalline the composition, and is reusable, response speed is fast, highly sensitive, measurement range extensively, does not need frequent check yet.This membraneous material can be prepared into a kind of lightweight solid hydrogen sensor, and energy consumption is low, and usage range is wide, not examined environmental constraints, the density of hydrogen scope of measurement is wide, because alloy film material granularity little (being approximately about 100nm), to hydrogen susceptibility height, thereby sensitivity is good.This hydrogen gas sensor can be used to measure density of hydrogen in the environment, as quality monitoring; Also can be used for monitoring the density of hydrogen of surrounding environment in production, transportation and the use, prevent to exceed standard.
Description of drawings
Fig. 1 is the alloy film material that utilizes physical gas-phase deposite method to make on the glass substrate sem photograph when not plating protective film.
Fig. 2 is the cross section sem photograph of Fig. 1.
Fig. 3 is the alloy film material that utilizes physical gas-phase deposite method to make on the silicon chip cross section sem photograph when not plating protective film.
Fig. 4 is the light transmittance curve of membraneous material of the present invention under different hydrogen concentration.
Embodiment
The invention will be further described below in conjunction with drawings and Examples.
Embodiment 1
With the induction melting method block magnesium, nickel are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 3Ni makes alloy film material 1 by magnetron sputtering on glass substrate 2, as depicted in figs. 1 and 2, alloy film material 1 thickness is 50nm, changes the Pd target, the protective film of evaporation 15nm (Pd film) on this alloy film material 1.Protective film does not show in Fig. 1 and Fig. 2, and the euphotic belt in the middle of Fig. 2 is the surface of alloy film material 1, because be with some angles during the scanning square section, this effect just occurs.Fig. 4 detects different density of hydrogen by the transmittance that detects this membraneous material, and the previous section of light transmittance curve is along with the increase of density of hydrogen, and it is very fast to rise, and aft section slowly descends along with the increase of density of hydrogen.
Embodiment 2
With the induction melting method block magnesium, nickel are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 2Ni makes alloy film material 1 by laser ablation on silicon chip 3, as shown in Figure 3, alloy film material 1 thickness is 50nm, changes the Pt target, the protective film of evaporation 20nm (Pt film) on this alloy film material 1.Protective film does not show in Fig. 3, and the euphotic belt of Fig. 3 is the surface of alloy film material 1, because scanning is with some angles during the square section, this effect just occurs.
Embodiment 3
With the induction melting method block magnesium, nickel are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 17Ni 3, on the thick nickel substrate of 2.5mm, make alloy film material by magnetron sputtering, alloy film material thickness is 1000nm, changes the Pd target, the protective film of evaporation 35nm on this alloy film material (Pd film).
Embodiment 4
With powder metallurgy process with magnesium, nickel by powder 650 ℃ of sintering 20 hours, behind the high annealing, be processed into alloys target with wire cutting method, the alloys target composition is Mg 19Ni makes alloy film material by electron beam evaporation plating on glass substrate, alloy film material thickness is 500nm, changes the Pt target, the protective film of evaporation 50nm on this alloy film material (Pt film).
Embodiment 5
With the method for piecing together target block magnesium, nickel are smelted into alloy-steel casting, are processed into alloys target with wire cutting method, the ratio of magnesium, nickel surface area is Mg on the alloy target surface 4Ni makes alloy film material by laser ablation on silicon chip, alloy film material thickness is 80nm, changes the Pt target, the protective film of evaporation 20nm on this alloy film material (Pt film).
Embodiment 6
With the induction melting method block magnesium, nickel and lanthanum are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 66La 33Ni makes alloy film material by magnetron sputtering on glass substrate, alloy film material thickness is 200nm, changes the Pd target, the protective film of evaporation 200nm on this alloy film material (Pd film).
Embodiment 7
With the induction melting method block magnesium, nickel and cerium are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 71Ce 24Ni 5, on the thick nickel substrate of 2.5mm, make alloy film material by magnetron sputtering, alloy film material thickness is 600nm, changes the Pd target, the protective film of evaporation 20nm on this alloy film material (Pd film).
Embodiment 8
With powder metallurgy process with magnesium, nickel and mishmetal powder 650 ℃ of sintering 20 hours, behind the high annealing, be processed into alloys target with wire cutting method, the alloys target composition is Mg 17Mm 2Ni makes alloy film material by electron beam evaporation plating on glass substrate, alloy film material thickness is 500nm, changes the Pt target, the protective film of evaporation 20nm on this alloy film material (Pt film).
Embodiment 9
With the method for piecing together target block magnesium, nickel, zirconium and yttrium are smelted into alloy-steel casting, are processed into alloys target with wire cutting method, the ratio of magnesium, nickel, zirconium, yttrium surface area is Mg on the alloy target surface 83Y 2Ni 12Zr 3, on silicon chip, make alloy film material by laser ablation, alloy film material thickness is 800nm, changes the Au target, the protective film of evaporation 20nm on this alloy film material (Pt film).
Embodiment 10
With the induction melting method block magnesium, nickel, titanium and aluminium are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 87A L5Ni 6Ti 2, on glass substrate, make alloy film material by magnetron sputtering, alloy film material thickness is 800nm, changes the Pd target, the protective film of evaporation 900nm on this alloy film material (Pd film).
Embodiment 11
With the induction melting method block magnesium, nickel, vanadium and cerium are smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting are processed into alloys target, the alloys target composition is Mg 91Ce 4Ni 4V makes alloy film material by magnetron sputtering on the thick nickel substrate of 2.5mm, alloy film material thickness is 600nm, changes Pd 2Ag 2The AuCo target, the protective film (Pd of evaporation 20nm on this alloy film material 2Ag 2The AuCo film).
Embodiment 12
With powder metallurgy process with magnesium, nickel, tin and drillings end 650 ℃ of sintering 20 hours, behind the high annealing, be processed into alloys target with wire cutting method, the alloys target composition is Mg 75Sn 2Ni 21Co 2, on glass substrate, make alloy film material by electron beam evaporation plating, alloy film material thickness is 500nm, changes Pt 5Ag 3Au 2The Co target, the protective film (Pt of evaporation 20nm on this alloy film material 5Ag 3Au 2The Co film).
Above-mentioned embodiment is the preferred embodiments of the present invention; can not limit claim of the present invention; other any change or other equivalent substitute mode that does not deviate from technical scheme of the present invention and made is included within protection scope of the present invention.

Claims (10)

1. thin film material used for hydrogen gas sensor, it is characterized in that: described membraneous material comprises substrate, alloy film material and protective film; Substrate and protective film folder are covering alloy film material; The basis of alloy film material is Mg and Ni, and chemical composition is Mg [p-x]α [x]Ni [1-y]β [y], wherein α is Al, Mn, Sn, Ca, Li, B, La, Ce, Nd, Pr, Y or mishmetal, wherein β is Cu, Ti, Co, Fe, Cr, Zr, V, Nb, Mo or W, wherein 2≤p≤70,0≤x≤35,0≤y≤0.8.
2. thin film material used for hydrogen gas sensor according to claim 1 is characterized in that: described substrate is metal, semiconductor or insulator substrate.
3. thin film material used for hydrogen gas sensor according to claim 1 is characterized in that: described protective film is Pd, Pt or Au film, the perhaps binary of Pd, Pt, Ag, Au, Co or complex alloy thin film.
4. thin film material used for hydrogen gas sensor according to claim 1 is characterized in that: described alloy film material thickness is 10～2000nm.
5. thin film material used for hydrogen gas sensor according to claim 1 is characterized in that: described protective film thickness is 2～1000nm.
6. the preparation method of the described thin film material used for hydrogen gas sensor of claim 1; it is characterized in that: at first with induction melting or powder metallurgy process prealloy target; use physical gas-phase deposite method then; on substrate, make alloy film material, then at alloy film material surface coverage one deck protective film.
7. the preparation method of thin film material used for hydrogen gas sensor according to claim 6, it is characterized in that: described physical gas-phase deposite method is sputter, electron beam evaporation plating or laser ablation method.
8. the preparation method of thin film material used for hydrogen gas sensor according to claim 6, it is characterized in that: the basis of described alloys target is Mg and Ni, chemical composition is Mg [p-x]α [x]Ni [1-y]β [y], wherein α is Al, Mn, Sn, Ca, Li, B, La, Ce, Nd, Pr, Y or mishmetal, wherein β is Cu, Ti, Co, Fe, Cr, Zr, V, Nb, Mo or W, wherein 2≤p≤70,0≤x≤35,0≤y≤0.8.
9. the preparation method of thin film material used for hydrogen gas sensor according to claim 8 is characterized in that: described alloys target is the potpourri of two kinds or two or more described chemical compositions.
10. the preparation method of thin film material used for hydrogen gas sensor according to claim 6 is characterized in that: with the induction melting method reguline metal is smelted into alloy-steel casting, behind the high annealing, with wire cutting method alloy-steel casting is processed into alloys target; Perhaps with powder metallurgy process with metal powder sintered, behind the high annealing, be processed into alloys target with wire cutting method.
CNA2007100312431A 2007-11-02 2007-11-02 Thin film material used for hydrogen gas sensor and preparation method thereof Pending CN101158662A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101831619A (en) * 2010-05-28 2010-09-15 浙江大学 Nano-crystalline Mg-Ni multilayer composite film and preparation method thereof
CN101545882B (en) * 2009-04-29 2012-05-30 杭州超距科技有限公司 Method for preparing gas sensor
CN103649736A (en) * 2011-07-15 2014-03-19 斯沃奇集团研究和开发有限公司 Hydrogen sensor with an active layer and method of manufacturing hydrogen sensors
CN104181202A (en) * 2014-08-13 2014-12-03 中国电子科技集团公司第四十八研究所 Multi-redundancy hydrogen sensor
CN105116024A (en) * 2015-08-31 2015-12-02 中国电子科技集团公司第四十八研究所 Online monitoring system for hydrogen in power transformer oil based on thin film technology
CN106018490A (en) * 2016-05-13 2016-10-12 湖北大学 Palladium-silver nano-film hydrogen-sensitive element and manufacturing method
CN108120743A (en) * 2016-11-28 2018-06-05 天津大学 Gas sensor based on modified silicon nanowires and its preparation method and application
CN108956712A (en) * 2018-06-29 2018-12-07 五邑大学 ZnO nano crystalline substance enhances Si nano column array sensitive material and preparation method thereof and sensor
CN112903751A (en) * 2021-01-04 2021-06-04 吉林大学 Xylene gas sensor based on gold-palladium alloy modified SnS2 sensitive layer and preparation method thereof
CN113061839A (en) * 2021-04-28 2021-07-02 广州大学 Preparation method of resistance type nano-structure hydrogen sensor

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101545882B (en) * 2009-04-29 2012-05-30 杭州超距科技有限公司 Method for preparing gas sensor
CN101831619A (en) * 2010-05-28 2010-09-15 浙江大学 Nano-crystalline Mg-Ni multilayer composite film and preparation method thereof
CN109991284A (en) * 2011-07-15 2019-07-09 斯沃奇集团研究和开发有限公司 The method of the hydrogen gas sensor and production hydrogen gas sensor of active layer
CN103649736A (en) * 2011-07-15 2014-03-19 斯沃奇集团研究和开发有限公司 Hydrogen sensor with an active layer and method of manufacturing hydrogen sensors
CN104181202A (en) * 2014-08-13 2014-12-03 中国电子科技集团公司第四十八研究所 Multi-redundancy hydrogen sensor
CN104181202B (en) * 2014-08-13 2017-03-15 中国电子科技集团公司第四十八研究所 A kind of many redundancy hydrogen gas sensors
CN105116024A (en) * 2015-08-31 2015-12-02 中国电子科技集团公司第四十八研究所 Online monitoring system for hydrogen in power transformer oil based on thin film technology
CN106018490A (en) * 2016-05-13 2016-10-12 湖北大学 Palladium-silver nano-film hydrogen-sensitive element and manufacturing method
CN108120743A (en) * 2016-11-28 2018-06-05 天津大学 Gas sensor based on modified silicon nanowires and its preparation method and application
CN108956712A (en) * 2018-06-29 2018-12-07 五邑大学 ZnO nano crystalline substance enhances Si nano column array sensitive material and preparation method thereof and sensor
CN108956712B (en) * 2018-06-29 2021-01-12 五邑大学 ZnO nanocrystal enhanced Si nanorod array sensitive material, preparation method thereof and sensor
CN112903751A (en) * 2021-01-04 2021-06-04 吉林大学 Xylene gas sensor based on gold-palladium alloy modified SnS2 sensitive layer and preparation method thereof
CN112903751B (en) * 2021-01-04 2021-11-12 吉林大学 SnS based on gold-palladium alloy modification2Xylene gas sensor of sensitive layer and preparation method thereof
CN113061839A (en) * 2021-04-28 2021-07-02 广州大学 Preparation method of resistance type nano-structure hydrogen sensor

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