CN104374817A - Broad-band gap Schottky diode hydrogen sensor chip and preparation method thereof - Google Patents
Broad-band gap Schottky diode hydrogen sensor chip and preparation method thereof Download PDFInfo
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- CN104374817A CN104374817A CN201410611721.6A CN201410611721A CN104374817A CN 104374817 A CN104374817 A CN 104374817A CN 201410611721 A CN201410611721 A CN 201410611721A CN 104374817 A CN104374817 A CN 104374817A
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Abstract
The invention relates to a hydrogen sensor chip and in particular relates to a broad-band gap Schottky diode hydrogen sensor chip and a preparation method thereof. The broad-band gap Schottky diode hydrogen sensor chip provided by the invention sequentially comprises a substrate, a dielectric layer and a hydrogen sensitive layer, wherein the dielectric layer is a hafnium oxide film. The response time of the hydrogen sensor chip is less than 20 seconds, and the lower limit of the hydrogen concentration can be detected to be 50ppm, so that the chip has potential application value in the field of hydrogen sensors.
Description
Technical field
The present invention relates to a kind of hydrogen gas sensor core body, particularly relate to a kind of broad-band gap 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 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, usual use silicon chip, hydrogen sensitive layer uses Metal Palladium and alloy thereof usually, the research of dielectric layer mainly concentrates in the oxide material such as silicon dioxide and alundum (Al2O3), the hydrogen gas sensor core body response time that this kind of material is made is long, and the concentration limit value detecting hydrogen is high.
Summary of the invention
The present invention seeks to, a kind of broad-band gap schottky diode hydrogen gas sensor core body and preparation method thereof is provided, long to overcome the hydrogen gas sensor core body response time in prior art, detect the defect that the concentration limit value of hydrogen is high.
One of technical scheme of the present invention is, provide described broad-band gap schottky diode hydrogen gas sensor core body, comprise substrate, dielectric layer and hydrogen sensitive layer successively, described dielectric layer is HfO_2 film.
Further, the thickness of described HfO_2 film is 2 ~ 20 nm.
Further, described hydrogen sensitive layer is Metal Palladium nickel alloy.
Further, described substrate is N-type silicon chip.
Further, the resistivity of described N-type silicon chip is 0.1 ~ 20 Ω cm.
Two of technical scheme of the present invention is, provides the preparation method of above-mentioned broad-band gap 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. HfO_2 film is prepared at substrate surface again;
C. on HfO_2 film, hydrogen sensitive layer is prepared.
Further, the method preparing HfO_2 film in described step b is magnetron sputtering, ion beam sputtering or pulsed laser deposition.
Further, the method preparing hydrogen sensitive layer in described step c is magnetron sputtering, ion beam sputtering, pulsed laser deposition, thermal evaporation or electron beam evaporation.
The k value of hafnium oxide is up to 25, and band gap width, also up to 5.8 eV, has chemically stable stability between the HfO_2 film of sputtering sedimentation and silicon chip, and and there is between silicon chip chemically stable stability, and do not produce any middle layer between silicon chip.In addition, larger band gap be conducive to reduce leakage current, with Si compensate for slower can be with large.Therefore, the HfO_2 film of high k value and broad-band gap is a kind of dielectric layer material of good schottky diode hydrogen gas sensor.
The principle of work of this schottky diode hydrogen gas sensor is: hydrogen adsorption is behind the surface of palladium-nickel alloy hydrogen sensitive layer, and under its catalytic action, hydrogen molecule decomposes generation hydrogen atom, and hydrogen atom diffuses through metal film, reaches metal-dielertric 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 palladium-nickel alloy, 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.
Beneficial effect of the present invention: the response time of this schottky diode hydrogen gas sensor core body is less than 20 s, can detect density of hydrogen lower limit is 50 ppm, show that it has potential using value in hydrogen gas sensor field.
Accompanying drawing explanation
Fig. 1 is the sectional view of broad-band gap schottky diode hydrogen gas sensor core body provided by the invention.
Embodiment
Below in conjunction with Fig. 1, the present invention is further described in detail.As shown in Figure 1, the core body of described a kind of broad-band gap schottky diode hydrogen gas sensor comprises the substrate 1 that resistivity is the phosphorus doping N-type silicon of 2 ~ 4 Ω cm, substrate 1 surface arranges the dielectric layer 2 that HfO_2 film is made, dielectric layer 2 surface arranges palladium-nickel alloy (wherein, the nickel of 13.6 wt%, the palladium of 86.4 wt%) the hydrogen sensitive layer 3 made of film.
The detailed process of the preparation method of above-mentioned core body is: use the acetone of purity assay, absolute ethyl alcohol to distinguish ultrasonic cleaning N-type silicon chip 5 min successively; The natural oxidizing layer on N-type silicon chip 1 surface is fallen again with the HF solution corrosion of mass percent concentration 10 %; With surperficial 5 min of deionized water rinsing N-type silicon chip 1, then dry up with nitrogen; The method of ion beam sputtering is utilized on N-type silicon chip 1, to prepare the HfO_2 film of 6 nm thickness as dielectric layer 2; The method of ion beam sputtering is utilized to prepare the palladium-nickel alloy of 60 nm thickness as hydrogen sensitive layer 3.
Above-mentioned core body is made hydrogen gas sensor, finds that its response time is 19.2 s after tested, can detect density of hydrogen lower limit is 50 ppm.
Claims (8)
1. a broad-band gap schottky diode hydrogen gas sensor core body, comprises substrate (1), dielectric layer (2) and hydrogen sensitive layer (3) successively, it is characterized in that: described dielectric layer (2) is HfO_2 film.
2. core body as claimed in claim 1, is characterized in that: the thickness of described HfO_2 film is 2 ~ 20 nm.
3. core body as claimed in claim 1, is characterized in that: described hydrogen sensitive layer (3) is Metal Palladium nickel alloy.
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. the preparation method of core body as described in claim 1-5, comprises the following steps successively:
A. first clean substrate surfaces, then remove the oxide layer of substrate surface;
B. HfO_2 film is prepared at substrate surface again;
C. on HfO_2 film, hydrogen sensitive layer is prepared.
7. preparation method as claimed in claim 6, is characterized in that: the method preparing HfO_2 film in described step b is magnetron sputtering, ion beam sputtering or pulsed laser deposition.
8. preparation method as claimed in claim 6, is characterized in that: the method preparing hydrogen sensitive layer in described step c is magnetron sputtering, ion beam sputtering, pulsed laser deposition, thermal evaporation or electron beam evaporation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410611721.6A CN104374817A (en) | 2014-11-04 | 2014-11-04 | Broad-band gap Schottky diode hydrogen sensor chip and preparation method thereof |
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| CN201410611721.6A CN104374817A (en) | 2014-11-04 | 2014-11-04 | Broad-band gap Schottky diode hydrogen sensor chip and preparation method thereof |
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| CN104374817A true CN104374817A (en) | 2015-02-25 |
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| CN201410611721.6A Pending CN104374817A (en) | 2014-11-04 | 2014-11-04 | Broad-band gap Schottky diode hydrogen sensor chip and preparation method thereof |
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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 |
| CN113406161A (en) * | 2021-06-03 | 2021-09-17 | 中国电子科技集团公司第四十八研究所 | Hydrogen sensor core body and preparation method thereof and hydrogen sensor |
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2014
- 2014-11-04 CN CN201410611721.6A patent/CN104374817A/en active Pending
Cited By (4)
| 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 |
| CN112858440B (en) * | 2021-02-04 | 2023-06-06 | 哈尔滨工业大学 | Schottky diode hydrogen sensor core |
| CN113406161A (en) * | 2021-06-03 | 2021-09-17 | 中国电子科技集团公司第四十八研究所 | Hydrogen sensor core body and preparation method thereof and hydrogen sensor |
| CN113406161B (en) * | 2021-06-03 | 2024-04-02 | 中国电子科技集团公司第四十八研究所 | Hydrogen sensor core, preparation method thereof and hydrogen sensor |
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Application publication date: 20150225 |
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