WO2014088403A1 - A resistive gas sensor device - Google Patents

A resistive gas sensor device Download PDF

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Publication number
WO2014088403A1
WO2014088403A1 PCT/MY2013/000225 MY2013000225W WO2014088403A1 WO 2014088403 A1 WO2014088403 A1 WO 2014088403A1 MY 2013000225 W MY2013000225 W MY 2013000225W WO 2014088403 A1 WO2014088403 A1 WO 2014088403A1
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WO
WIPO (PCT)
Prior art keywords
layer
gas sensor
sensor device
nanowires
electrodes
Prior art date
Application number
PCT/MY2013/000225
Other languages
French (fr)
Inventor
Daniel Chia Sheng Bien
Aun Shih Teh
Hing Wah Lee
Wai Yee Lee
Khairul Anuar ABD WAHID
Original Assignee
Mimos Berhad
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Publication of WO2014088403A1 publication Critical patent/WO2014088403A1/en

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    • 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
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y15/00—Nanotechnology for interacting, sensing or actuating, e.g. quantum dots as markers in protein assays or molecular motors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02587—Structure
    • H01L21/0259—Microstructure
    • H01L21/02603—Nanowires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/02636—Selective deposition, e.g. simultaneous growth of mono- and non-monocrystalline semiconductor materials
    • H01L21/02653—Vapour-liquid-solid growth

Definitions

  • the present invention relates to a resistive gas sensor device and a method of fabricating the resistive gas sensor device.
  • Typical gas sensor devices comprise thin film sensing membrane on top of a microhotplate platform where the microhotplate is used to heat up the sensing membrane to a few hundred degrees Celsius to improve device sensitivity.
  • microhotplates are considered active devices which are of high power consumption, hence not feasible for continuous monitoring.
  • a resistive gas sensor device wherein the gas sensor device operates based on changes in electrical resistivity using nanomaterials interconnectable by conductive bridge electrodes between contact electrodes.
  • a method of fabricating a resistive gas sensor device characterized in that, the method includes the steps of depositing an insulating layer on a silicon substrate layer, depositing a conductive metal layer onto the insulating layer, depositing a thin metallic catalyst layer covering a surface of the conductive metal layer and etching the metal catalyst layer and growing nanostructures from the metal catalyst layer that is exposed, such that the nanostructures are interconnected with each other and the conductive metal layer.
  • Figure 1 shows a cross sectional view of a resistive gas sensor device in the present embodiment of the invention
  • Figure 2 shows a flowchart showing a method of fabricating a resistive gas sensor device in the present embodiment of the invention
  • Figure 3 shows a top view of contact electrodes in the preferred embodiment of the invention
  • Figure 4 shows a cross sectional view of the device in the method of fabricating the same in the present invention
  • Figure 5 shows a cross sectional view of the method of fabrication in an alternative embodiment of the invention.
  • Figure 6 shows a cross sectional view of the device illustrating that the insulating layer may be etched further to form high aspect ratio trenches.
  • the present invention relates to a method of fabricating a resistive gas sensor device and a resistive gas sensor device.
  • this specification will describe the present invention according to the preferred embodiment of the present invention.
  • limiting the description to the preferred embodiment of the invention is merely to facilitate discussion of the present invention and it is envisioned that those skilled in the art may devise various modifications and equivalents without departing from the scope of the appended claims.
  • Figure 2 illustrates a method of fabricating a resistive gas sensor device.
  • the method includes the steps of depositing an insulating layer (105) on a silicon substrate layer (101), depositing a conductive metal layer (103) onto the insulating layer (105), depositing a thin metallic catalyst layer (107) covering a surface of the conductive metal layer (103) and etching the metal catalyst layer (107) and growing nanostructures (109) from the metal catalyst layer (107) that is exposed, such that the nanostructures (109) are interconnected with each other and the conductive metal layer (103).
  • the insulating layer (105) is constructed of silicon dioxide or silicon nitride deposited by physical or chemical vapour deposition (PVD or CVD) or silicon dioxide grown by thermal oxidation method.
  • the oxide/nitride layer acts to isolate conductive metal bridge and contact electrodes from underlying silicon substrate layer (101) ( Figure 4a).
  • the conductive metal layer (103) is deposited onto the oxide/nitride surface by either PVD or CVD method to form the bridge and contact electrodes ( Figure 4b).
  • This conductive metal layer (103) needs to be able to withstand high growth temperature of nanomaterials such as, but not restricted to nanotubes, nanowires and graphene, which is typically above 300 °C.
  • the material(s) can be selected from a group including but not limited to gold, platinum, and tungsten.
  • a thin metal catalyst layer (107) is deposited to cover the surface of the bridge electrodes and in between the bridges ( Figure 4c).
  • the metal catalyst (107) type will depend on the required nanomaterial such as, carbon nanotubes, graphene, tungsten oxide nanowires, zinc oxide nanowires, indium oxide nanowires, tin oxide nanowires, or combination thereof.to grow carbon nanotubes and graphene and gold catalyst to grow zinc oxide (ZnO) and tin oxide (Sn0 2 ) nanowires.
  • the nanomaterials are used to grow nanostructures (109) on the thin metal catalyst layer (107).
  • the nanomaterials are of vertical or multidirectional arrays.
  • the nanostructures (109) are grown from exposed metal catalyst (107) on and in between the bridge electrodes ( Figure 4d).
  • the nanostructures (109) are interconnected within themselves and with the bridge electrodes to form connectivity between the contact electrodes.
  • an alternative growth method is to deposit the metal catalyst only on top surface of the bridge electrode. This allows the nanomaterials to laterally grow across the bridge electrodes hence connecting the electrodes with one another.
  • the insulating layer (105) can be etched further to form high aspect ratio trenches prior to metal catalyst deposition and nanomaterial growth (Figure 6).
  • an alternative to growing nanomaterial directly onto the silicon substrate layer (101) as described above is to drop cast or spin coat the nanomaterial onto the bridge electrodes. If an insulator type substrate is used the initial oxide or nitride insulating layer will not be required.
  • the method describes connecting the contact electrodes, by insulating the substrate material to provide electrical isolation, forming the conductive bridge and contact electrodes, depositing metal catalyst on top of the bridge electrode surface, and growing of nanomaterial using the metal catalyst layer.
  • Figure 1 shows cross section of a resistive gas sensor device that is fabricated using the method as described above.
  • the resistive gas sensor device operates based on changes in electrical resistivity using nanomaterials interconnectable by conductive bridge electrodes between contact electrodes.
  • the device is of passive type which operates based on a change in electrical resistance when receptive ions are detected by the nanomaterial.
  • the device includes at least one pair of conductive contact electrodes for electrical connection, an array of conductive bridge electrodes in between the contact electrodes and an array of nanomaterial covering a top surface and in between the bridge electrode.
  • Typical nanomaterials that are associated with gas sensors include carbon nanotubes, graphene, ZnO nanowires and Sn02 nanowires. As the nanotubes and nanowires are typically short, the bridge electrodes acts as a link to connect them together. Without nanomaterials, the electrical connections between the contact electrodes are of open circuit. As most nanowires used for gas sensing are of semiconductor materials, the bridge electrodes helps to improve the overall device conductivity and response time.
  • the bridge electrodes must not cause electrical shorting between the contact electrodes and can have a design of but not limited to isolated square or circular islands (Figure 3a); long electrode structures which are disconnected from the main contacts (Figure 3b) and alternating long electrode structures connecting to one of the main contacts (Figure 3c).
  • the invention is an improvement over typical gas sensor devices as the use of nanomaterials such as nanotube, nanowire, grapheme, as new sensing elements, now allows passive type gas sensing platform to be developed. This is because the high surface to volume ratio of these nanomaterials improves device sensitivity without heating to elevated temperatures, unlike those of the prior art.
  • This invention is adapted for chemical gas detection.
  • the disclosed invention is suitable, but not restricted to, for use in agriculture, environmental monitoring, biomedical and industrial processes.

Abstract

A resistive gas sensor device, wherein the gas sensor device operates based on changes in electrical resistivity using nanomaterials interconnectable by conductive bridge electrodes between contact electrodes.

Description

A RESISTIVE GAS SENSOR DEVICE
FIELD OF INVENTION The present invention relates to a resistive gas sensor device and a method of fabricating the resistive gas sensor device.
BACKGROUND OF INVENTION Chemical gas detection has many applications in agriculture, environmental monitoring, biomedical and industrial processes. Typical gas sensor devices comprise thin film sensing membrane on top of a microhotplate platform where the microhotplate is used to heat up the sensing membrane to a few hundred degrees Celsius to improve device sensitivity. However, microhotplates are considered active devices which are of high power consumption, hence not feasible for continuous monitoring.
US 2009/0151429 describes a resistive gas sensor device that uses a microheater as a platform. However, this prior art does not address the problem of high power consumption which is not ideal for monitoring.
Therefore, there is a need for an alternative method of producing and using gas sensors without heating to high temperatures. SUMMARY OF INVENTION
Accordingly, there is provided a resistive gas sensor device, wherein the gas sensor device operates based on changes in electrical resistivity using nanomaterials interconnectable by conductive bridge electrodes between contact electrodes.
Further, there is provided a method of fabricating a resistive gas sensor device, characterized in that, the method includes the steps of depositing an insulating layer on a silicon substrate layer, depositing a conductive metal layer onto the insulating layer, depositing a thin metallic catalyst layer covering a surface of the conductive metal layer and etching the metal catalyst layer and growing nanostructures from the metal catalyst layer that is exposed, such that the nanostructures are interconnected with each other and the conductive metal layer. The present invention consists of several novel features and a combination of parts hereinafter fully described and illustrated in the accompanying description and drawings, it being understood that various changes in the details may be made without departing from the scope of the invention or sacrificing any of the advantages of the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
The present invention will be fully understood from the detailed description given herein below and the accompanying drawings which are given by way of illustration only, and thus are not limitative of the present invention, wherein:
Figure 1 shows a cross sectional view of a resistive gas sensor device in the present embodiment of the invention;
Figure 2 shows a flowchart showing a method of fabricating a resistive gas sensor device in the present embodiment of the invention; Figure 3 shows a top view of contact electrodes in the preferred embodiment of the invention;
Figure 4 shows a cross sectional view of the device in the method of fabricating the same in the present invention;
Figure 5 shows a cross sectional view of the method of fabrication in an alternative embodiment of the invention; and
Figure 6 shows a cross sectional view of the device illustrating that the insulating layer may be etched further to form high aspect ratio trenches.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention relates to a method of fabricating a resistive gas sensor device and a resistive gas sensor device. Hereinafter, this specification will describe the present invention according to the preferred embodiment of the present invention. However, it is to be understood that limiting the description to the preferred embodiment of the invention is merely to facilitate discussion of the present invention and it is envisioned that those skilled in the art may devise various modifications and equivalents without departing from the scope of the appended claims.
The following detailed description of the preferred embodiment will now be described in accordance with the attached drawings, either individually or in combination. Figure 2 illustrates a method of fabricating a resistive gas sensor device. The method includes the steps of depositing an insulating layer (105) on a silicon substrate layer (101), depositing a conductive metal layer (103) onto the insulating layer (105), depositing a thin metallic catalyst layer (107) covering a surface of the conductive metal layer (103) and etching the metal catalyst layer (107) and growing nanostructures (109) from the metal catalyst layer (107) that is exposed, such that the nanostructures (109) are interconnected with each other and the conductive metal layer (103).
The insulating layer (105) is constructed of silicon dioxide or silicon nitride deposited by physical or chemical vapour deposition (PVD or CVD) or silicon dioxide grown by thermal oxidation method. The oxide/nitride layer acts to isolate conductive metal bridge and contact electrodes from underlying silicon substrate layer (101) (Figure 4a). The conductive metal layer (103) is deposited onto the oxide/nitride surface by either PVD or CVD method to form the bridge and contact electrodes (Figure 4b). This conductive metal layer (103) needs to be able to withstand high growth temperature of nanomaterials such as, but not restricted to nanotubes, nanowires and graphene, which is typically above 300 °C. The material(s) can be selected from a group including but not limited to gold, platinum, and tungsten.
A thin metal catalyst layer (107) is deposited to cover the surface of the bridge electrodes and in between the bridges (Figure 4c). The metal catalyst (107) type will depend on the required nanomaterial such as, carbon nanotubes, graphene, tungsten oxide nanowires, zinc oxide nanowires, indium oxide nanowires, tin oxide nanowires, or combination thereof.to grow carbon nanotubes and graphene and gold catalyst to grow zinc oxide (ZnO) and tin oxide (Sn02) nanowires. The nanomaterials are used to grow nanostructures (109) on the thin metal catalyst layer (107). The nanomaterials are of vertical or multidirectional arrays.
The nanostructures (109) are grown from exposed metal catalyst (107) on and in between the bridge electrodes (Figure 4d). The nanostructures (109) are interconnected within themselves and with the bridge electrodes to form connectivity between the contact electrodes.
As shown in Figure 5, an alternative growth method is to deposit the metal catalyst only on top surface of the bridge electrode. This allows the nanomaterials to laterally grow across the bridge electrodes hence connecting the electrodes with one another. To allow further gas penetration beneath the nanomaterial, the insulating layer (105) can be etched further to form high aspect ratio trenches prior to metal catalyst deposition and nanomaterial growth (Figure 6). Also, as an alternative to growing nanomaterial directly onto the silicon substrate layer (101) as described above is to drop cast or spin coat the nanomaterial onto the bridge electrodes. If an insulator type substrate is used the initial oxide or nitride insulating layer will not be required.
The method describes connecting the contact electrodes, by insulating the substrate material to provide electrical isolation, forming the conductive bridge and contact electrodes, depositing metal catalyst on top of the bridge electrode surface, and growing of nanomaterial using the metal catalyst layer.
Figure 1 shows cross section of a resistive gas sensor device that is fabricated using the method as described above. The resistive gas sensor device operates based on changes in electrical resistivity using nanomaterials interconnectable by conductive bridge electrodes between contact electrodes.
The device is of passive type which operates based on a change in electrical resistance when receptive ions are detected by the nanomaterial. The device includes at least one pair of conductive contact electrodes for electrical connection, an array of conductive bridge electrodes in between the contact electrodes and an array of nanomaterial covering a top surface and in between the bridge electrode. Typical nanomaterials that are associated with gas sensors include carbon nanotubes, graphene, ZnO nanowires and Sn02 nanowires. As the nanotubes and nanowires are typically short, the bridge electrodes acts as a link to connect them together. Without nanomaterials, the electrical connections between the contact electrodes are of open circuit. As most nanowires used for gas sensing are of semiconductor materials, the bridge electrodes helps to improve the overall device conductivity and response time. The bridge electrodes must not cause electrical shorting between the contact electrodes and can have a design of but not limited to isolated square or circular islands (Figure 3a); long electrode structures which are disconnected from the main contacts (Figure 3b) and alternating long electrode structures connecting to one of the main contacts (Figure 3c). The invention is an improvement over typical gas sensor devices as the use of nanomaterials such as nanotube, nanowire, grapheme, as new sensing elements, now allows passive type gas sensing platform to be developed. This is because the high surface to volume ratio of these nanomaterials improves device sensitivity without heating to elevated temperatures, unlike those of the prior art.
This invention is adapted for chemical gas detection. The disclosed invention is suitable, but not restricted to, for use in agriculture, environmental monitoring, biomedical and industrial processes.

Claims

1. A resistive gas sensor device, wherein the gas sensor device operates based on changes in electrical resistivity using nanomaterials interconnectable by conductive bridge electrodes between contact electrodes.
2. The device as claimed in claim 1 , wherein the nanomaterial covers a top surface of the bridge electrodes and in between the bridge electrodes.
3. The device as claimed in claim 1 , wherein the nanomaterial includes carbon nanotubes, conductive nanowires, semiconductor nanowires, nanoporous structures or grapheme.
4. A method of fabricating a resistive gas sensor device, characterized in that, the method includes the steps of: i. depositing an insulating layer (105) on a silicon substrate layer (101);
ii. depositing a conductive metal layer (103) onto the insulating layer (105);
iii. depositing a thin metallic catalyst layer (107) covering a surface of the conductive metal layer (103) and etching the metal catalyst layer (107); and iv. growing nanostructures (109) from the metal catalyst layer (107) that is exposed,
such that the nanostructures (109) are interconnected with each other and the conductive metal layer (103).
5. The method as claimed in claim 4, wherein the insulating layer (105) is an oxide/nitride layer.
6. The method as claimed in claim 4, wherein the conductive metal layer (103) forms bridge and contact electrodes. The method as claimed in claim 4, wherein the nanomaterials is selected from a group consisting and not limited to carbon nanotubes, graphene, tungsten oxide nanowires, zinc oxide nanowires, indium oxide nanowires, tin oxide nanowires, or combination thereof.
PCT/MY2013/000225 2012-12-07 2013-12-03 A resistive gas sensor device WO2014088403A1 (en)

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Cited By (9)

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WO2015193645A1 (en) * 2014-06-19 2015-12-23 Applied Nanodetectors Ltd. Gas sensors and gas sensor arrays
CN105510390A (en) * 2016-01-18 2016-04-20 郑州轻工业学院 Multi-stage structure nanometer In2O3/graphene composite and preparation method and application thereof
CN107345818A (en) * 2017-06-29 2017-11-14 上海集成电路研发中心有限公司 A kind of preparation method of graphene-based sensor
AT519492A1 (en) * 2016-12-22 2018-07-15 Mat Center Leoben Forschung Gmbh Sensor arrangement for determining and optionally measuring a concentration of a plurality of gases and method for producing a sensor arrangement
CN109142467A (en) * 2018-07-23 2019-01-04 杭州电子科技大学 A kind of high sensitive NO2Gas sensor and preparation method thereof
LU100442B1 (en) * 2017-09-19 2019-03-19 Luxembourg Inst Science & Tech List Gas sensor device with high sensitivity at low temperature and method of fabrication thereof
AT521213A1 (en) * 2018-05-04 2019-11-15 Mat Center Leoben Forschung Gmbh Method for producing a sensor and sensor manufactured therewith
CN112713181A (en) * 2020-12-28 2021-04-27 光华临港工程应用技术研发(上海)有限公司 Preparation method of gas sensor and gas sensor
CN114354724A (en) * 2022-01-11 2022-04-15 山西大学 Metal oxide semiconductor gas sensor and preparation method and application thereof

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WO2008153593A1 (en) * 2006-11-10 2008-12-18 Bourns Inc. Nanomaterial-based gas sensors
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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015193645A1 (en) * 2014-06-19 2015-12-23 Applied Nanodetectors Ltd. Gas sensors and gas sensor arrays
CN105510390A (en) * 2016-01-18 2016-04-20 郑州轻工业学院 Multi-stage structure nanometer In2O3/graphene composite and preparation method and application thereof
CN105510390B (en) * 2016-01-18 2019-01-04 郑州轻工业学院 A kind of multilevel structure nanometer In2O3/ graphene composite material and its preparation method and application
AT519492A1 (en) * 2016-12-22 2018-07-15 Mat Center Leoben Forschung Gmbh Sensor arrangement for determining and optionally measuring a concentration of a plurality of gases and method for producing a sensor arrangement
AT519492B1 (en) * 2016-12-22 2019-03-15 Mat Center Leoben Forschung Gmbh Sensor arrangement for determining and optionally measuring a concentration of a plurality of gases and method for producing a sensor arrangement
CN107345818A (en) * 2017-06-29 2017-11-14 上海集成电路研发中心有限公司 A kind of preparation method of graphene-based sensor
CN107345818B (en) * 2017-06-29 2020-05-15 上海集成电路研发中心有限公司 Preparation method of graphene-based sensor
WO2019057786A1 (en) * 2017-09-19 2019-03-28 Luxembourg Institute Of Science And Technology (List) Gas sensor device with high sensitivity at low temperature and method of fabrication thereof
LU100442B1 (en) * 2017-09-19 2019-03-19 Luxembourg Inst Science & Tech List Gas sensor device with high sensitivity at low temperature and method of fabrication thereof
CN111108371A (en) * 2017-09-19 2020-05-05 卢森堡科学技术研究院 Gas sensor device having high sensitivity at low temperature and method for manufacturing same
AT521213A1 (en) * 2018-05-04 2019-11-15 Mat Center Leoben Forschung Gmbh Method for producing a sensor and sensor manufactured therewith
AT521213B1 (en) * 2018-05-04 2022-12-15 Mat Center Leoben Forschung Gmbh Method of making a sensor and sensor made therewith
CN109142467A (en) * 2018-07-23 2019-01-04 杭州电子科技大学 A kind of high sensitive NO2Gas sensor and preparation method thereof
CN112713181A (en) * 2020-12-28 2021-04-27 光华临港工程应用技术研发(上海)有限公司 Preparation method of gas sensor and gas sensor
CN112713181B (en) * 2020-12-28 2022-08-05 光华临港工程应用技术研发(上海)有限公司 Preparation method of gas sensor and gas sensor
CN114354724A (en) * 2022-01-11 2022-04-15 山西大学 Metal oxide semiconductor gas sensor and preparation method and application thereof
CN114354724B (en) * 2022-01-11 2022-11-22 山西大学 Metal oxide semiconductor gas sensor and preparation method and application thereof

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