CN104374819A - Multi-layer film Schottky diode hydrogen sensor core body and preparation method thereof - Google Patents
Multi-layer film Schottky diode hydrogen sensor core body and preparation method thereof Download PDFInfo
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- CN104374819A CN104374819A CN201410611746.6A CN201410611746A CN104374819A CN 104374819 A CN104374819 A CN 104374819A CN 201410611746 A CN201410611746 A CN 201410611746A CN 104374819 A CN104374819 A CN 104374819A
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Abstract
The invention relates to the field of hydrogen sensors, and in particular relates to a multi-layer film Schottky diode hydrogen sensor core body and a preparation method thereof. The multi-layer film Schottky diode hydrogen sensor core body sequentially comprises a substrate, a first dielectric layer and a hydrogen sensitive layer, wherein a poly Schiff base thin film is additionally arranged between the first dielectric layer and the hydrogen sensitive layer as a second dielectric layer. The core body is prepared into a hydrogen sensor, the sensitivity of the multi-layer film Schottky diode hydrogen sensor core body is more than 56mV under the hydrogen concentration of 2000ppm, the detected lower limit of the hydrogen concentration is 5ppm, and the characteristics show that the multi-layer film Schottky diode hydrogen sensor core body disclosed by the invention has potential application values in the field of hydrogen sensing.
Description
Technical field
The present invention relates to hydrogen gas sensor field, particularly relate to a kind of multilayer film schottky diode hydrogen gas sensor core body and preparation method thereof.
Background technology
Hydrogen, as a kind of clean energy resource of high burning efficiency, is widely applied in the assist system of Aero-Space, vehicle and boats and ships etc.; Meanwhile, hydrogen, as a kind of important reducibility gas and carrier gas, also plays extremely important effect in fields such as chemical industry, electronics, medical treatment.But hydrogen is a kind of inflammable and explosive hazardous gas, when aerial content is between 4-75%, runs into naked light and namely explode.Hydrogen molecule diameter is very little and colourless, tasteless, easily leaks and not easily discovers, thus bringing very large potential safety hazard, threaten personal safety as well as the property safety in the process produced, store, transport and use.Therefore, development is used for the highly sensitive hydrogen gas sensor of density of hydrogen and hydrogen gas leakage in testing environment, and become the problem of people's growing interest, the development of high performance hydrogen gas sensor also becomes one of the emphasis in sensor research field at present.
Current hydrogen gas sensor is mainly based on the resistor-type hydrogen gas sensor of palladium or palldium alloy material and based on the semi-conductor type hydrogen gas sensor of schottky diode, mos capacitance and MOS transistor etc.Compared to resistor-type hydrogen gas sensor, semi-conductor type hydrogen gas sensor generally has fast response time, detect the advantages such as the low and sensitivity of density of hydrogen lower limit is large.
The sensitive core body of hydrogen gas sensor is the core component of hydrogen gas sensor, is mainly used to detect density of hydrogen.The core body of hydrogen gas sensor generally includes three layers: substrate, dielectric layer, hydrogen sensitive layer.Utilize the change of the electric potential difference between hydrogen sensitive layer and substrate to detect hydrogen.Substrate uses semiconductor material, and usually use silicon chip, hydrogen sensitive layer uses Metal Palladium and alloy thereof usually.At present, the research of dielectric layer mainly concentrates in the oxide materials such as silicon dioxide, and it is low that this kind of material exists hydrogen gas sensor sensitivity as dielectric layer, detects the problem of the lower limit for height of density of hydrogen.
Summary of the invention
The present invention seeks to, a kind of multilayer film schottky diode hydrogen gas sensor core body and preparation method thereof is provided, low to solve hydrogen gas sensor sensitivity in prior art, detect the problem of the lower limit for height of density of hydrogen.
One of technical scheme of the present invention is, provide described multilayer film schottky diode hydrogen gas sensor core body, comprise substrate, first medium layer and hydrogen sensitive layer successively, between first medium layer and hydrogen sensitive layer, increase polyschiff's base film is second dielectric layer.
Further, described poly-Schiff-Base film thickness is 3 ~ 15 nm.
Further, described first medium layer thickness is 2 ~ 10 nm.
Further, described substrate is N-type silicon chip.
Further, the resistivity of described N-type silicon chip is 0.1 ~ 20 Ω cm.
Further, described first medium layer is titanium dioxide, aluminium oxide or silicon oxide film.
Further, described hydrogen sensitive layer is palladium or palldium alloy.
Further, the preferred palladium evanohm of described palldium alloy.
Two of technical scheme of the present invention is, provides the preparation method of described multilayer film schottky diode hydrogen gas sensor core body, comprises the following steps successively:
A. first clean substrate surfaces, then remove the oxide layer of substrate surface;
B. first medium layer is prepared at substrate surface again;
C. dissolved by polyschiff's base, it is second dielectric layer that described first medium layer is prepared polyschiff's base film;
D. in second dielectric layer, hydrogen sensitive layer is prepared.
Further, the method preparing polyschiff's base film in described step c is coated with for dripping, spraying or spin coating one or more.
The method that substrate is prepared titanium deoxid film comprises magnetron sputtering, ion beam sputtering, pulsed laser deposition, by power during control sputtering and time, by the THICKNESS CONTROL of titanium deoxid film between 2 ~ 10 nm.The method preparing the processing of polyschiff's base film use solution is: polyschiff's base is dissolved in solvent, again by one or more modes of dripping in painting, spraying, spin coating, by controlling concentration, the coating speed of poly-Schiff-Base solution and applying number of times, by the THICKNESS CONTROL of poly-Schiff-Base film between 3 ~ 15 nm.
The method that polyschiff's base film is prepared palladium evanohm hydrogen sensitive layer film comprises magnetron sputtering, ion beam sputtering, pulsed laser deposition, thermal evaporation and electron beam evaporation, power during by controlling sputtering or evaporating and time, by the THICKNESS CONTROL of palladium evanohm film between 15 ~ 100 nm.Palladium evanohm hydrogen sensitive layer adopts the method for photoetching or hard mask plate to obtain different shapes.
The principle of work of this schottky diode hydrogen gas sensor is: hydrogen adsorption is behind the surface of hydrogen sensitive layer, and under its catalytic action, hydrogen molecule decomposes generation hydrogen atom, and hydrogen atom diffuses through metal film, reaches hydrogen sensitive layer-dielectric layer interface.Under the attraction of interfacial charge, hydrogen atom is attracted to the interface of metal-dielertric, is formed with dipole layer, and this dipole layer, by changing the work function of hydrogen sensitive layer, causes the potential barrier of schottky diode to reduce, and the I-V characteristic of schottky diode sends drift.Therefore, test at constant current, the drift of output voltage is the response signal of sensor to hydrogen, and along with the increasing of density of hydrogen, the drift value of output voltage also responds increase.
Above-mentioned hydrogen sensitive layer selects the metal containing palladium usually, and simple metal palladium absorbs in hydrogen process and can become fragile and even break, and generally selects palldium alloy as hydrogen sensitive layer.
Beneficial effect of the present invention: the present invention increases poly-Schiff-Base film as second dielectric layer, under the density of hydrogen of 2000 ppm, the sensitivity of this multilayer film schottky diode hydrogen gas sensor core body is greater than 56 mV, can detect density of hydrogen lower limit is 5 ppm, these characteristics show that the present invention has potential using value at hydrogen sensory field.
Accompanying drawing explanation
The sectional view of Fig. 1 multilayer film schottky diode provided by the invention hydrogen gas sensor core body.
Embodiment
As shown in Figure 1, described a kind of multilayer film schottky diode hydrogen gas sensor core body comprises substrate 1, first medium layer 2, second dielectric layer 3, hydrogen sensitive layer 4.Wherein, N-type silicon chip selected by substrate 1, N-type silicon chip surface arranges the first medium layer 2 that titanium deoxid film is made, and first medium layer 2 surface arranges the second dielectric layer 3 that poly-Schiff-Base film is made, and second dielectric layer 3 surface arranges palladium evanohm film and makes hydrogen sensitive layer 4.
The preparation method of above-mentioned core body in turn includes the following steps: phosphorus doping N-type silicon chip 5 min by the acetone of purity assay, absolute ethyl alcohol ultrasonic cleaning resistivity being 0.1 ~ 20 Ω cm successively; Fall the natural oxidizing layer on N-type silicon chip surface again with the HF solution corrosion of mass percent concentration 10 %, with deionized water rinsing N-type silicon substrate surface, then use nitrogen gun silicon wafer blow-drying; The method of recycling ion beam sputtering prepares the titanium deoxid film of 3 nm thickness as first medium layer 2 in N-type silicon chip; Again poly-Schiff-Base is dissolved in N, N-dimethyl acetamide, is made into the solution of mass percent concentration 2%; Then on first medium layer 2 surface with rotating speed spin coating 10 s of 800 rpm, then dry in the vacuum drying oven of 100 DEG C, obtain poly-Schiff-Base film, gained film thickness is about 7 nm, formed second dielectric layer 3; Recycling ion beam sputtering prepares the palladium evanohm (wherein, the chromium of 17.5 wt%, the palladium of 82.5 wt%) of 60 nm thickness as hydrogen sensitive layer 4 at poly-Schiff-Base film surface.
The hydrogen gas sensor core body of above-mentioned preparation is made hydrogen gas sensor test, obtaining sensitivity is 56.4 mV, detects density of hydrogen lower limit is 5 ppm.
Claims (10)
1. a multilayer film schottky diode hydrogen gas sensor core body, comprise substrate (1), first medium layer (2) and hydrogen sensitive layer (4) successively, it is characterized in that: between first medium layer (2) and hydrogen sensitive layer (4), increase polyschiff's base film is second dielectric layer (3).
2. core body as claimed in claim 1, is characterized in that: described poly-Schiff-Base film thickness is 3 ~ 15 nm.
3. core body as claimed in claim 1, is characterized in that: described first medium layer (2) thickness is 2 ~ 10 nm.
4. core body as claimed in claim 1, is characterized in that: described substrate (1) is N-type silicon chip.
5. core body as claimed in claim 4, is characterized in that: the resistivity of described N-type silicon chip is 0.1 ~ 20 Ω cm.
6. core body as claimed in claim 1, is characterized in that: described first medium layer (2) is titanium dioxide, aluminium oxide or silicon oxide film.
7. core body as claimed in claim 1, is characterized in that: described hydrogen sensitive layer (4) is palladium or palldium alloy.
8. core body as claimed in claim 7, is characterized in that: the preferred palladium evanohm of described palldium alloy.
9. the preparation method of core body as described in claim 1-8, comprises the following steps:
A. first clean substrate surfaces, then remove the oxide layer of substrate surface;
B. first medium layer is prepared at substrate surface again;
C. dissolved by polyschiff's base, it is second dielectric layer that described first medium layer is prepared polyschiff's base film;
D. in second dielectric layer, hydrogen sensitive layer is prepared.
10. preparation method as claimed in claim 9, is characterized in that: the method preparing polyschiff's base film in described step c is drip one or more in painting, spraying, spin coating.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112858440A (en) * | 2021-02-04 | 2021-05-28 | 哈尔滨工业大学 | Schottky diode hydrogen sensor core |
| CN116046871A (en) * | 2023-02-16 | 2023-05-02 | 兰州大学 | Hydrogen sensor core body with heterostructure |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US6027954A (en) * | 1998-05-29 | 2000-02-22 | The United States Of America As Represented By The Administrator Of The National Aeronautics And Space Administration | Gas sensing diode and method of manufacturing |
| TW385366B (en) * | 1998-06-05 | 2000-03-21 | Nat Science Council | Hydrogen-sensitive palladium (Pd) membrane/semiconductor Schottky diode sensor |
| JP2002122560A (en) * | 2000-08-10 | 2002-04-26 | Ngk Spark Plug Co Ltd | Gas sensor |
| TWI274152B (en) * | 2004-11-05 | 2007-02-21 | Univ Nat Cheng Kung | Hydrogen sensor device and method for fabricating the same |
| US7389675B1 (en) * | 2006-05-12 | 2008-06-24 | The United States Of America As Represented By The National Aeronautics And Space Administration | Miniaturized metal (metal alloy)/ PdOx/SiC hydrogen and hydrocarbon gas sensors |
| JP5836935B2 (en) * | 2009-05-29 | 2015-12-24 | メルク パテント ゲゼルシャフト ミット ベシュレンクテル ハフツングＭｅｒｃｋ Ｐａｔｅｎｔ Ｇｅｓｅｌｌｓｃｈａｆｔ ｍｉｔ ｂｅｓｃｈｒａｅｎｋｔｅｒ Ｈａｆｔｕｎｇ | Conjugated polymers and their use as organic semiconductors |
| CN102980915B (en) * | 2012-11-08 | 2015-02-18 | 清华大学 | Preparation method of palladium-doped TiO2 nano-tube array Schottky junction hydrogen-sensitive sensor |
| CN103779350A (en) * | 2014-02-25 | 2014-05-07 | 中国电子科技集团公司第四十九研究所 | Schottky diode hydrogen sensor core and manufacturing method of core |
| CN204287106U (en) * | 2014-11-04 | 2015-04-22 | 中国电子科技集团公司第四十八研究所 | A kind of multilayer film schottky diode hydrogen gas sensor core body |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112858440A (en) * | 2021-02-04 | 2021-05-28 | 哈尔滨工业大学 | Schottky diode hydrogen sensor core |
| CN112858440B (en) * | 2021-02-04 | 2023-06-06 | 哈尔滨工业大学 | Schottky diode hydrogen sensor core |
| CN116046871A (en) * | 2023-02-16 | 2023-05-02 | 兰州大学 | Hydrogen sensor core body with heterostructure |
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