CN204287106U - A kind of multilayer film schottky diode hydrogen gas sensor core body - Google Patents

A kind of multilayer film schottky diode hydrogen gas sensor core body Download PDF

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CN204287106U
CN204287106U CN201420651439.6U CN201420651439U CN204287106U CN 204287106 U CN204287106 U CN 204287106U CN 201420651439 U CN201420651439 U CN 201420651439U CN 204287106 U CN204287106 U CN 204287106U
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hydrogen
core body
gas sensor
hydrogen gas
schottky diode
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陈浩
谢贵久
景涛
曹勇全
陈伟
龚星
曹勇飞
易航
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CETC 48 Research Institute
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Abstract

The utility model relates to hydrogen gas sensor field, particularly relates to a kind of multilayer film schottky diode hydrogen gas sensor core body.Described multilayer film schottky diode hydrogen gas sensor core body, comprises substrate, first medium layer and hydrogen sensitive layer successively, and between first medium layer and hydrogen sensitive layer, increase poly-Schiff-Base film is second dielectric layer.Above-mentioned core body is made hydrogen gas sensor, 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 utility model has potential using value at hydrogen sensory field.

Description

A kind of multilayer film schottky diode hydrogen gas sensor core body
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.
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 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.
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 poly-Schiff-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.
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 poly-Schiff-Base film use solution is: poly-Schiff-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 poly-Schiff-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 (8)

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 poly-Schiff-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.
CN201420651439.6U 2014-11-04 2014-11-04 A kind of multilayer film schottky diode hydrogen gas sensor core body Withdrawn - After Issue CN204287106U (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105466976A (en) * 2015-12-11 2016-04-06 中国电子科技集团公司第四十八研究所 Dielectric material for hydrogen sensor core, hydrogen sensor core as well as preparation method and application of hydrogen sensor core
CN104374819B (en) * 2014-11-04 2017-03-15 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 and preparation method thereof
CN107884453A (en) * 2017-11-13 2018-04-06 青海民族大学 A kind of TiO 2 nanotubes modified array Schottky junction hydrogen sensor of palladium and preparation method thereof
CN111474214A (en) * 2020-04-29 2020-07-31 青岛菲灿新材料科技服务有限责任公司 Graphene-based high-sensitivity hydrogen sensor and preparation method thereof

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104374819B (en) * 2014-11-04 2017-03-15 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 and preparation method thereof
CN105466976A (en) * 2015-12-11 2016-04-06 中国电子科技集团公司第四十八研究所 Dielectric material for hydrogen sensor core, hydrogen sensor core as well as preparation method and application of hydrogen sensor core
CN105466976B (en) * 2015-12-11 2018-04-17 中国电子科技集团公司第四十八研究所 Hydrogen gas sensor core dielectric material, hydrogen gas sensor core and preparation method and application
CN107884453A (en) * 2017-11-13 2018-04-06 青海民族大学 A kind of TiO 2 nanotubes modified array Schottky junction hydrogen sensor of palladium and preparation method thereof
CN111474214A (en) * 2020-04-29 2020-07-31 青岛菲灿新材料科技服务有限责任公司 Graphene-based high-sensitivity hydrogen sensor and preparation method thereof

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