CN116046871A - Hydrogen sensor core body with heterostructure - Google Patents
Hydrogen sensor core body with heterostructure Download PDFInfo
- Publication number
- CN116046871A CN116046871A CN202310125402.3A CN202310125402A CN116046871A CN 116046871 A CN116046871 A CN 116046871A CN 202310125402 A CN202310125402 A CN 202310125402A CN 116046871 A CN116046871 A CN 116046871A
- Authority
- CN
- China
- Prior art keywords
- hydrogen
- hydrogen sensor
- sensor core
- heterostructure
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000001257 hydrogen Substances 0.000 title claims abstract description 80
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 80
- 125000004435 hydrogen atom Chemical class [H]* 0.000 title claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 41
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000758 substrate Substances 0.000 claims abstract description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 5
- 229910001020 Au alloy Inorganic materials 0.000 claims abstract description 4
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 4
- 239000003353 gold alloy Substances 0.000 claims abstract description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000012528 membrane Substances 0.000 claims 3
- 150000002431 hydrogen Chemical class 0.000 abstract description 36
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052763 palladium Inorganic materials 0.000 abstract description 18
- 229910052751 metal Inorganic materials 0.000 abstract description 14
- 239000002184 metal Substances 0.000 abstract description 14
- 229910052697 platinum Inorganic materials 0.000 abstract description 7
- 230000004044 response Effects 0.000 description 13
- 238000001514 detection method Methods 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000004549 pulsed laser deposition Methods 0.000 description 3
- 230000035945 sensitivity Effects 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910006339 Si—Pb Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 230000016507 interphase Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 239000011540 sensing material Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01M—TESTING STATIC OR DYNAMIC BALANCE OF MACHINES OR STRUCTURES; TESTING OF STRUCTURES OR APPARATUS, NOT OTHERWISE PROVIDED FOR
- G01M3/00—Investigating fluid-tightness of structures
- G01M3/02—Investigating fluid-tightness of structures by using fluid or vacuum
- G01M3/04—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point
- G01M3/16—Investigating fluid-tightness of structures by using fluid or vacuum by detecting the presence of fluid at the leakage point using electric detection means
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/4071—Cells and probes with solid electrolytes for investigating or analysing gases using sensor elements of laminated structure
Abstract
The invention relates to a hydrogen sensor core body with a heterostructure, which is capable of detecting ppb concentration at room temperature and comprises a substrate, a sensitive film and a medium layer positioned between the substrate and the sensitive film. The sensitive film is a metal palladium film or a palladium-gold alloy film or a metal platinum film, and the thickness of the sensitive film is 100-200nm; the dielectric layer is a silicon oxide layer or an aluminum oxide layer or a silicon nitride layer, and the thickness of the dielectric layer is 30-50nm; the substrate is N-type silicon, P-type silicon or undoped silicon wafer. The hydrogen sensor constructed based on the core has the characteristics of small volume, low cost and low required temperature, and can monitor the hydrogen with ppb level concentration at room temperature.
Description
Technical Field
The application relates to the technical field of hydrogen sensing, in particular to a hydrogen sensor core body based on a Si-Pb heterostructure.
Background
Due to hydrogen (H) 2 ) Has high energy density and combustion heat, and the combustion products are harmless, and become the main stream fuel in the aerospace field. In order to cope with urgent requirements for real-time monitoring of hydrogen fuel in the process of aerospace operation, the high ppb hydrogen under the influence of temperature, humidity and various atmospheres in real complex environments is broken throughThe key technologies of sensitivity detection and reduction of the lower limit of hydrogen detection are used for realizing accurate detection of ppb-level concentration hydrogen, and a low-dimensional nano hydrogen sensing material with low lower limit of detection and strong environmental adaptability is needed to be developed. The existing gas sensor mainly has the defects of high detection lower limit, long response time, easiness in interference by other external gases (such as water vapor, CO and the like) and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a heterostructure hydrogen sensor core body capable of rapidly detecting the height of an adjustable Schottky barrier of the hydrogen concentration.
The hydrogen sensor core body of the heterostructure is capable of detecting ppb concentration at room temperature and comprises a substrate, a sensitive film and a dielectric layer positioned between the substrate and the sensitive film.
Further, the hydrogen sensor core body disclosed by the application is characterized in that the sensitive film is a metal palladium film or a palladium-gold alloy film. The 4d electron layer of palladium lacks two electrons and is capable of forming an unstable chemical bond with hydrogen (this reaction of palladium with hydrogen is reversible), under the action of palladium, hydrogen is ionized into protons with a radius of 1.5 x 10 -15 m, and palladium has a lattice constant of 3.88×10 －10 m (20 ℃ C.), hydrogen can exist in the palladium lattice, palladium and hydrogen form hydrogen palladium under the hydrogen environment, when the hydrogen environment is removed, protons are combined with electrons and form hydrogen molecules again under the action of palladium, and the hydrogen palladium also changes back to the original palladium, and the change of the palladium lattice caused by hydrogen injection can be irreversible when the hydrogen concentration is too large. Thus, the overflow effect of Pb metal catalytically cleaves H2 molecules into H atoms and combines with them into PdHx (0)<x<0.7 According to different values of x, the work function can be adjusted within the range of 3.2-5.27eV, so that the height of a Pd/Si Schottky barrier is changed, the electric transport characteristic of a Pd/Si heterostructure is changed, and high-sensitivity sensing of H2 is realized.
Further, the hydrogen sensor core body is characterized in that the sensitive film is a metal platinum film. The 5d electron layer of platinum lacks one electron and is also capable of catalytically cracking hydrogen and oxygen. Under the action of platinum, hydrogen is ionized into hydrogen atoms, oxygen molecules are ionized into oxygen atoms, the catalytic process is similar to that of metal palladium, hydrogen and oxygen in platinum metal regulate the work function of the metal palladium, the Schottky barrier height of Pt/Si is changed, and therefore the electric transport characteristic of a heterostructure is changed.
Further, the hydrogen sensor core body disclosed by the application has the thickness of the sensitive film of 100-200nm. Too large or too small thickness can affect the sensing performance of the hydrogen sensor to a certain extent, and when the thickness is less than 100nm, although the hydrogen sensor is easy to sense low-concentration hydrogen, the thickness of the metal film is uneven, so that the stability of the device is affected. Conversely, when the thickness is greater than 200nm, the detection of the concentration of hydrogen at ppb level is affected.
Further, in the hydrogen sensor core, the dielectric layer is a silicon oxide layer, an aluminum oxide layer or a silicon nitride layer, and the thickness of the dielectric layer is 30-50nm. The dielectric layer is mainly used for improving the stability of the heterostructure, and the thickness of the dielectric layer also has a certain influence on the performance of the sensor. When the dielectric layer is too thick, the bias voltage of the sensor core body can not enable current to pass through the heterojunction interface, and the change of the electric transport characteristic caused by the change of the hydrogen concentration can not be detected; when the dielectric layer is too thin, it cannot isolate the silicon and palladium from each other, possibly causing interphase breakdown short circuit and damaging the device.
Further, in the hydrogen sensor core described herein, the substrate is N-type silicon, P-type silicon, or undoped silicon wafer.
The beneficial effects of this application include:
the hydrogen sensor core fully utilizes the overflow effect of metal Pb to lead H to be 2 The molecule is catalytically cleaved into H atoms and combined with them to form PdHx (0)<x<0.7 According to different values of x, the work function can be adjusted within the range of 3.2-5.27eV, thereby changing the height of the Pd/Si Schottky barrier, changing the electric transport characteristic of the Pd/Si heterostructure and realizing H-junction 2 Is a high sensitivity sensor of (a). The hydrogen sensor constructed based on the core has the characteristics of small volume, low cost and low required temperature, and can monitor the hydrogen with ppb concentration at room temperatureAnd (3) air. The leakage phenomenon of each link such as hydrogen preparation, storage and transportation, use and the like can be discovered early, and the characteristic of quick response is particularly suitable for monitoring the leakage of the aerospace fuel. The hydrogen sensor based on the core body has response time of 100s-110s and recovery time of about 300s for an atmosphere with hydrogen concentration of 200ppb, and the lower detection limit of the hydrogen concentration can reach 20ppb.
Drawings
FIG. 1 is a schematic diagram of a hydrogen sensor core and a test system according to the present invention;
FIG. 2 is a plot of the voltammogram of a hydrogen sensor core in an air environment and an environment with hydrogen in accordance with example 1 of the present invention;
FIG. 3 is a graph showing the response of the hydrogen sensor core of example 1 of the present invention to 200ppb hydrogen at a fixed bias at room temperature;
FIG. 4 is a graph showing the response of the hydrogen sensor core described in example 2 of the present invention to 200ppb hydrogen at a fixed bias at room temperature.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not specified in the specific embodiments and are carried out according to conventional conditions or conditions suggested by the manufacturer.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used in the description herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The hydrogen sensor core body of the heterostructure is capable of detecting ppb concentration at room temperature, and comprises a substrate, a sensitive film and a dielectric layer positioned between the substrate and the sensitive film. The sensitive film is a metal palladium film or a palladium-gold alloy film or a metal platinum film, and the thickness of the sensitive film is 100-200nm; the dielectric layer is a silicon oxide layer or an aluminum oxide layer or a silicon nitride layer, and the thickness of the dielectric layer is 30-50nm; the substrate is N-type silicon, P-type silicon or undoped silicon wafer.
The specific preparation method of the hydrogen sensor core body with the heterostructure comprises the following steps:
firstly, preprocessing a silicon wafer which is required as a substrate material, and cutting the silicon wafer into a fixed size and a fixed shape; then forming a layer of compact oxide film on the surface of the silicon wafer by using a silicon thermal oxidation process, namely treating a dielectric layer; and then, metal is coated on the substrate in a radio frequency sputtering mode, so that the hydrogen sensor core body with small volume, low cost and simple structure is obtained. The hydrogen sensor based on the core of the present application has low operating temperature and fast response time, wherein the response is defined as (I g -I 0 )/I 0 ,I 0 For the current of the device operating in air, I g The device is operated under the current of the hydrogen environment with certain concentration. The lower limit of detection for the hydrogen concentration can reach 20ppb.
Example 1:
the heterostructure hydrogen sensor core in this embodiment 1 includes a substrate and a sensitive film, and a dielectric layer between the substrate and the sensitive film. The sensitive film is a metal palladium film, and the thickness of the sensitive film is 100nm; the dielectric layer is silicon oxide, and the thickness of the dielectric layer is 50nm; the substrate is an N-type silicon wafer. The test condition in fig. 2 is a triangle wave with 0.01Hz amplitude of 5V, and the IV curve of the device under the same test condition under the environment conditions of simulated air and 200ppb hydrogen, so that the current difference of the device under the 3.4V voltage in two atmospheres is the largest, so that the test condition in fig. 3 is that the bias voltage of 3.4V is added to the two ends of the device, the response value of the concentration of 200ppb hydrogen is measured to be 65%, and the response time is 100s; the test temperature of the whole device is room temperature, and as the test temperature increases, the sensitivity of the hydrogen sensor to the hydrogen environment decreases, and the response to the hydrogen decreases.
Example 2:
this embodiment 2 differs from embodiment 1 only in that: the sensitive film is a metal platinum film, and the thickness of the sensitive film is 100nm; platinum is deposited on the surface of a silicon wafer by using Pulsed Laser Deposition (PLD), and the PLD has the advantage that the film thickness and the film flatness can be accurately controlled when a film with the thickness of less than 150nm is deposited. The test condition is also triangular wave with 0.01Hz amplitude of 5V, the IV curve of the device under the environment condition of simulated air and 200ppb hydrogen can be measured under the same test condition, and the optimal test bias voltage is 2V; since platinum metal also has a catalytic cracking effect on oxygen, the effect of oxygen is large when detecting low concentration hydrogen, and the response value of the concentration of 200ppb hydrogen is 26 s and the response time is 110s under the optimal test bias. The test temperature of the whole device is room temperature, the intrinsic carrier concentration in silicon is increased along with the increase of the test temperature, the Schottky barrier height is reduced, the influence of hydrogen on the current transport characteristic of the heterostructure is reduced, and the response of the device to hydrogen is reduced.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.
Claims (6)
1. A heterostructure hydrogen sensor core, characterized in that the hydrogen sensor core is a hydrogen sensor core capable of detecting ppb level concentration at room temperature, the hydrogen sensor core comprising a substrate and a sensitive film, and a dielectric layer between the substrate and the sensitive film.
2. The heterostructure hydrogen sensor core of claim 1, wherein the sensitive membrane is a metallic palladium membrane or a palladium-gold alloy membrane.
3. The heterostructure hydrogen sensor core of claim 1, wherein the sensitive film is a metallic platinum film.
4. A heterostructure hydrogen sensor core according to claim 2 or 3, characterized in that the sensitive film thickness is 100-200nm.
5. The heterostructure hydrogen sensor core of claim 4, wherein the dielectric layer is a silicon oxide or aluminum oxide or silicon nitride layer, and the dielectric layer is 30-50nm thick.
6. The heterostructure hydrogen sensor core of claim 5, wherein the substrate is N-type silicon, P-type silicon or undoped silicon wafer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310125402.3A CN116046871A (en) | 2023-02-16 | 2023-02-16 | Hydrogen sensor core body with heterostructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310125402.3A CN116046871A (en) | 2023-02-16 | 2023-02-16 | Hydrogen sensor core body with heterostructure |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116046871A true CN116046871A (en) | 2023-05-02 |
Family
ID=86133084
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310125402.3A Pending CN116046871A (en) | 2023-02-16 | 2023-02-16 | Hydrogen sensor core body with heterostructure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116046871A (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN205562452U (en) * | 2015-12-11 | 2016-09-07 | 中国电子科技集团公司第四十八研究所 | Hydrogen sensor is dielectric material , hydrogen sensor core for core |
-
2023
- 2023-02-16 CN CN202310125402.3A patent/CN116046871A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN205562452U (en) * | 2015-12-11 | 2016-09-07 | 中国电子科技集团公司第四十八研究所 | Hydrogen sensor is dielectric material , hydrogen sensor core for core |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6935158B2 (en) | MIS hydrogen sensors | |
| Soo et al. | Advances of SiC-based MOS capacitor hydrogen sensors for harsh environment applications | |
| Brunet et al. | Comparison of the gas sensing performance of SnO2 thin film and SnO2 nanowire sensors | |
| Parmar et al. | Copper (II) oxide thin film for methanol and ethanol sensing | |
| Ushio et al. | Effects of interface states on gas-sensing properties of a CuO/ZnO thin-film heterojunction | |
| Williams et al. | NOx response of tin dioxide based gas sensors | |
| JP2007163253A (en) | Hydrogen gas sensor | |
| Kim et al. | Enhanced hydrogen sensing properties of Pd-coated SnO2 nanorod arrays in nitrogen and transformer oil | |
| von Wenckstern et al. | pn‐Heterojunction diodes with n‐type In2O3 | |
| WO2018143016A1 (en) | Gas sensor | |
| US20200300825A1 (en) | Gas Sensor Device With High Sensitivity At Low Temperature And Method Of Fabrication Thereof | |
| US20100005853A1 (en) | Continuous Range Hydrogen Sensor | |
| Kang et al. | A New Hydrogen Sensor Using a Polycrystalline Diamond‐Based Schottky Diode | |
| US6293137B1 (en) | Hydrogen sensor | |
| US20020020853A1 (en) | Gas sensor | |
| US6378355B2 (en) | Combustible gas diode sensor | |
| Rajan et al. | An investigation on electrical and hydrogen sensing characteristics of RF sputtered ZnO thin-film with palladium Schottky contacts | |
| CN116046871A (en) | Hydrogen sensor core body with heterostructure | |
| Chen et al. | Comparison of Y-doped Bazro3 thin films for high temperature humidity sensors by RF sputtering and pulsed laser deposition | |
| Tsai et al. | Investigation on a Pd–AlGaN/GaN Schottky diode-type hydrogen sensor with ultrahigh sensing responses | |
| Kim et al. | Ultra-thin filmed SnO 2 gas sensor with a low-power micromachined hotplate for selective dual gas detection of carbon monoxide and methane | |
| Chen et al. | Pulsed laser deposited Y-doped BaZrO3 thin films for high temperature humidity sensors | |
| Zampiceni et al. | Thermal treatment stabilization processes in SnO/sub 2/thin films catalyzed with Au and Pt | |
| Taher et al. | High electron mobility transistor-based hydrogen sensor using ITO as a sensing layer | |
| Gurbuz et al. | A PECVD diamond device for chemical gas sensing applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |