CN113447530B - Gas sensing device - Google Patents

Gas sensing device Download PDF

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CN113447530B
CN113447530B CN202110219193.XA CN202110219193A CN113447530B CN 113447530 B CN113447530 B CN 113447530B CN 202110219193 A CN202110219193 A CN 202110219193A CN 113447530 B CN113447530 B CN 113447530B
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oxide
gas
power supply
metal oxide
drain electrode
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CN113447530A (en
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程纲
郭俊猛
甘家辉
阮浩然
杜祖亮
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Henan University
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Henan University
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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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

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Abstract

The invention discloses a gas sensing device, which comprises: the plasma device comprises a first power supply, a plasma module and a gas induction module. The first power supply is used for providing direct current of more than 30 volts and less than 8000 volts; the plasma module is connected with the negative electrode of the first power supply and is used for discharging by utilizing direct current; the gas induction module is arranged corresponding to the plasma module, is connected with the first power supply and is used for reacting with the plasma module to generate an ionization phenomenon; the gas induction module comprises a source electrode, a drain electrode, metal oxide and an insulating substrate; a source electrode, a drain electrode and a metal oxide are carried on the surface of the insulating substrate, and the metal oxide is arranged between the source electrode and the drain electrode; the source electrode is connected with a second direct current power supply, the drain electrode is connected with the anode of the first power supply, and the drain electrode and the anode of the first power supply are both connected with the ground. The invention realizes gas detection at room temperature and improves the gas detection sensitivity.

Description

Gas sensing device
Technical Field
The invention relates to the technical field of sensors, in particular to a gas sensing device.
Background
The resistance type gas sensor based on the metal oxide can detect various gases, has wide application in industrial production and daily life, and has the advantages of low cost, high detection speed, small volume, portability and the like. However, in the prior art, the gas sensor based on metal oxide needs to realize gas sensing under the condition of high working temperature (100-. The mechanism of operation of metal oxide based gas sensors is as follows: surface adsorbed O 2 - The plasma and the detection gas are subjected to oxidation reaction, and after the reaction, O 2 - The released electrons return to the oxide, so that the current of the oxide is increased, and the gas is detected. Under this operating regime, the sensitivity of detection (i.e., the ratio of change in current) is related to the surface O 2 - The adsorption amount of the active ions and the adsorption type are closely related. However, this process is a thermally activated process and requires a high temperature to increase the electron concentration at the oxide surface. And at room temperature, limited by the low surface electron concentration, O 2 - The adsorption on the surface of the oxide shows a higher adsorption barrier, so that O 2 - And more active O - (O 2- ) The amount of ion adsorption is small, whichIs the root cause of the inability of metal oxide based gas sensors to achieve room temperature gas sensing. Therefore, how to activate the adsorption amount and the adsorption type of the surface active ions of the metal oxide at room temperature, so as to improve the gas detection sensitivity at room temperature and realize accurate detection of gas is a key scientific problem which needs to be solved urgently at present.
Disclosure of Invention
The invention aims to provide a gas sensing device to realize gas detection at room temperature and improve gas detection sensitivity.
To achieve the above object, the present invention provides a gas sensing apparatus comprising:
a first power supply for providing a direct current greater than 30 volts and less than 8000 volts;
the plasma module is connected with the negative electrode of the first power supply and used for discharging by utilizing the direct current;
the gas induction module is arranged corresponding to the plasma module, is connected with the first power supply and is used for reacting with the plasma module to generate an ionization phenomenon;
the gas induction module comprises a source electrode, a drain electrode, metal oxide and an insulating substrate; the source electrode, the drain electrode, and the metal oxide are mounted on a surface of the insulating substrate, and the metal oxide is provided between the source electrode and the drain electrode;
the source electrode is connected with a second direct current power supply, the drain electrode is connected with the anode of the first power supply, and the drain electrode and the anode of the first power supply are both connected with the ground.
Optionally, air with a relative humidity greater than 10% and less than 70% is between the plasma module and the gas induction module.
Optionally, the first power source is a friction nano-generator device or a direct current pulse power source.
Optionally, the triboelectric nanogenerator device comprises:
a triboelectric nanogenerator for providing an alternating current of greater than 30 volts and less than 8000 volts;
and the rectifier bridge is respectively connected with the friction nano generator and the plasma module and is used for converting the alternating current into direct current.
Optionally, the metal oxide is zinc oxide, tin oxide, tungsten oxide, iron oxide, titanium oxide, copper oxide, indium oxide, cobalt oxide, vanadium oxide, chromium oxide, germanium oxide, manganese oxide, or zirconium oxide.
Optionally, the insulating substrate is made of silicon dioxide, silicon, glass, or ceramic.
Optionally, the source electrode and the drain electrode are both made of Cr/Au.
Optionally, the plasma module is a tungsten needle with a radius of curvature greater than 0.1 μm and less than 500 μm.
According to the specific embodiment provided by the invention, the invention discloses the following technical effects:
the invention discloses a gas sensing device, which comprises: the plasma device comprises a first power supply, a plasma module and a gas induction module. The first power supply is used for providing direct current of more than 30 volts and less than 8000 volts; the plasma module is connected with the negative electrode of the first power supply and is used for discharging by utilizing direct current; the gas induction module is arranged corresponding to the plasma module, is connected with the first power supply and is used for reacting with the plasma module to generate an ionization phenomenon; the gas induction module comprises a source electrode, a drain electrode, metal oxide and an insulating substrate; a source electrode, a drain electrode, and a metal oxide are mounted on a surface of the insulating substrate, the metal oxide being provided between the source electrode and the drain electrode; the source electrode is connected with a second direct current power supply, the drain electrode is connected with the anode of the first power supply, and the drain electrode and the anode of the first power supply are both connected with the ground. The invention realizes gas detection at room temperature and improves gas detection sensitivity.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a block diagram of a gas sensing device according to an embodiment of the present invention;
FIG. 2 is a structural diagram of a gas sensing device including a friction nano-generator device according to an embodiment of the present invention;
FIG. 3 is a schematic diagram of a gas sensing device in accordance with an embodiment of the present invention;
FIG. 4 is a corona discharge current line graph of a gas sensing device in accordance with an embodiment of the present invention;
the device comprises a first power supply 1, a plasma module 2, a gas induction module 3 and a friction nano generator device 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention aims to provide a gas sensing device to realize gas detection at room temperature and improve gas detection sensitivity.
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with figures are described in further detail below.
Fig. 1 is a block diagram of a gas sensing device according to an embodiment of the present invention, and as shown in fig. 1, the gas sensing device includes: the plasma device comprises a first power supply 1, a plasma module 2, a gas induction module 3 and a second direct current power supply. The plasma module 2 is connected with the negative electrode of the first power supply 1; and the gas induction module 3 is arranged corresponding to the plasma module 2 and is connected with the first power supply 1. The first power supply 1 is used for providing direct current of more than 30 volts and less than 8000 volts; the plasma module 2 is used for discharging by using the direct current; the gas induction module 3 is used for reacting with the plasma module 2 to generate an ionization phenomenon. The gas induction module 3 comprises a source electrode, a drain electrode, metal oxide and an insulating substrate; the source electrode, the drain electrode, and the metal oxide are mounted on a surface of the insulating substrate, and the metal oxide is provided between the source electrode and the drain electrode; the source electrode is connected with a second direct current power supply. The second direct current power supply provides electric energy for the source electrode. The drain electrode is connected to ground. The drain electrode and the positive electrode of the first power source are both connected to ground. Air with relative humidity more than 10% and less than 70% is arranged between the plasma module 2 and the gas induction module 3.
In the embodiment of the present invention, the first power source 1 is a friction nano-generator device 4 or a high voltage dc power source. Fig. 2 is a structural diagram of a gas sensing device including a friction nano-generator device according to an embodiment of the present invention, and as shown in fig. 2, the friction nano-generator device 4 includes: a friction nano generator and a rectifier bridge. The triboelectric nanogenerator is used to provide an alternating current of greater than 30 volts and less than 8000 volts. And the rectifier bridge is respectively connected with the friction nano generator, the plasma module 2 and the source electrode and is used for converting the alternating current into direct current. The operation mode of the friction nanometer generator is any one of an independent layer mode, a single electrode mode, a horizontal sliding mode or a vertical contact-separation mode. The motion speed and the acceleration of the friction nano generator are respectively 0-1000m/s and 0-1000m/s 2 The discharge mode is alternating current, and the discharge distance is 0-80 mm. The voltage range of the direct current pulse power supply is 30-8000V. The rectifier bridge is a full-wave-band rectifier bridge.
The friction nano generator is used as a novel energy acquisition technology, can convert mechanical motion in the environment into electric energy, and has the advantages of low cost, simple processing, convenient use, large-scale production and the like. The friction nanometer generator has output voltage as high as kilovolt, and can easily drive air to discharge to generate plasma. Therefore, the friction nano generator, the adjustable pulse high-voltage power supply and the adjustable high-voltage direct-current power supply can activate the plasma module 2 to discharge in a humid air environment to generate active gas ions, and gas sensing at room temperature is further realized through interaction of the gas active ions and the gas to be detected.
In an embodiment of the present invention, the metal oxide is zinc oxide, tin oxide, tungsten oxide, iron oxide, titanium oxide, copper oxide, indium oxide, cobalt oxide, vanadium oxide, chromium oxide, germanium oxide, manganese oxide, or zirconium oxide. The insulating substrate is made of silicon dioxide, silicon, glass or ceramic. The source electrode and the drain electrode are both made of Cr/Au. The plasma module 2 is a tungsten needle with the curvature radius of 0.1-500 mu m. The invention uses photoetching technology and electron beam evaporation to carry the source electrode and the drain electrode on the surface of the insulating substrate. The metal oxide in the invention is a nano material. Metal oxide is grown over the insulating substrate, source and drain electrodes to form a gold-half contact.
The invention is used for the treatment of acetone, ethanol, benzene, formaldehyde, toluene, CO and NO 2 、NO、NH 3 、O 2 Or H 2 And S and the like.
The working process of the invention is as follows:
firstly, in an air environment with the relative humidity of 10-70%, the first power supply 1 applies direct current of more than 30 volts and less than 8000 volts to the plasma module 2, so that an ionization phenomenon is generated between the plasma module 2 and the gas induction module 3. FIG. 3 is a schematic diagram of a gas sensing device according to an embodiment of the present invention, as shown in FIG. 3, the ionization region generated by the ionization phenomenon is divided into a plasma region and a single-ion region, and the single-ion region can generate a large amount of O 2 - O having higher activity - 、OH - (H 2 O) n And (4) plasma active ions. And the active ions generated during the ionization process are adsorbed on the surface of the cathode (i.e., metal oxide). The plasma module 2 is a tungsten needle. During the gas discharge process, the discharge mode and the gas ion type can be controlled by adjusting the distance and the relative position between the tungsten needle tip and the drain electrode in the gas induction module 3. The discharge modes include spark discharge, glow discharge, corona discharge, and the like. Wherein the corona discharge current has a line diagram as shown in FIG. 4Shown in the figure. Different gas ion types refer to O at different distances and locations - 、OH - (H 2 O) n The proportion of plasma active ions varies. Then, the first power supply 1 is stopped to supply power, and the gas to be detected (which may contain acetone, ethanol, benzene, formaldehyde, toluene, CO, NO) is introduced between the plasma module and the gas induction module 3 2 、NO、NH 3 、O 2 Or H 2 S these harmful gases), OH adsorbed on metal oxide generated in ionization of single ion zone - (H 2 O) n And ions generate hydroxyl groups, so that the energy band of the metal oxide bends downwards, and more active oxygen ions on the surface of the metal oxide are induced to perform oxidation reaction with harmful gas components in the gas to be detected. After the reaction, electrons released by active oxygen ions return to the metal oxide, so that the current of the metal oxide is increased, and the gas is detected according to the change proportion of the detection current.
The invention has the following beneficial effects:
(1) the friction nano generator generates periodic reciprocating motion, periodic potential difference is generated between two groups of Cu electrodes of the friction nano generator, and the potential difference can generate gas discharge. The open-circuit voltage of the friction nano generator in the alternating current mode can reach 8kV through the rectifier bridge and is far larger than the threshold voltage of air discharge with different relative humidity, and plasma can be generated through gas discharge. The friction nano generator can fully utilize widely existing mechanical energy and avoid utilization and consumption of fossil resources. The invention can also adopt the traditional high-voltage direct-current power supply.
(2) The invention realizes the efficient gas detection at room temperature. No additional heating or other conditions are required. Almost all metal oxides have effects, and the gas-sensitive sensing material has wide sources. Easy separation and recovery and simple operation.
(3) The invention can simply realize gas detection at room temperature without adding noble metal or illumination.
(4) The invention has simple operation and low cost, and provides a new method for realizing room temperature gas sensing.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other. The principles and embodiments of the present invention have been described herein using specific examples, which are provided only to assist in understanding the core concepts of the present invention; meanwhile, for a person skilled in the art, according to the idea of the present invention, the specific embodiments and the application range may be changed. In view of the above, the present disclosure should not be construed as limiting the invention.

Claims (8)

1. A gas sensing device, comprising:
a first power supply for providing a direct current greater than 30 volts and less than 8000 volts;
the plasma module is connected with the negative electrode of the first power supply and is used for discharging by utilizing the direct current;
the gas induction module is arranged corresponding to the plasma module, is connected with the first power supply and is used for reacting with the plasma module to generate an ionization phenomenon;
the gas induction module comprises a source electrode, a drain electrode, metal oxide and an insulating substrate; the source electrode, the drain electrode, and the metal oxide are mounted on a surface of the insulating substrate, and the metal oxide is provided between the source electrode and the drain electrode;
the source electrode is connected with a second direct current power supply, the drain electrode is connected with the anode of the first power supply, and the drain electrode and the anode of the first power supply are both connected with the ground; carrying the source electrode and the drain electrode on the surface of the insulating substrate by utilizing a photoetching technology and electron beam evaporation; the metal oxide grows on the insulating substrate, the source electrode and the drain electrode to form gold-half contact;
the working process of the gas sensing device is as follows:
first, in an air environment with a relative humidity of 10-70%, the first power supply will be greater than 30 voltsAnd the direct current less than 8000V acts on the plasma module, so that the ionization phenomenon is generated between the plasma module and the gas induction module; the ionization region generated by the ionization phenomenon is divided into a plasma region and a single ion region, and the single ion region can generate a large amount of O 2 - O having better activity - 、OH - (H 2 O) n Active ions are adsorbed on the surface of the metal oxide, the first power supply is stopped, the gas to be detected is introduced between the plasma module and the gas induction module, and OH adsorbed on the metal oxide and generated in the ionized single-ion region - (H 2 O) n And ions generate hydroxyl groups, so that the energy band of the metal oxide bends downwards, more active oxygen ions on the surface of the metal oxide are induced to perform oxidation reaction with harmful gas components in the gas to be detected, electrons released by the active oxygen ions return to the metal oxide after the reaction, the current of the metal oxide is increased, and the gas is detected according to the change proportion of the detection current.
2. The gas sensing device of claim 1, wherein the relative humidity between the plasma module and the gas sensing module is greater than 10% and less than 70% air.
3. The gas sensing device of claim 1, wherein the first power source is a triboelectric nano-generator device or a direct current pulsed power source.
4. The gas sensing device of claim 3, wherein the triboelectric nanogenerator device comprises:
a triboelectric nanogenerator for providing an alternating current of greater than 30 volts and less than 8000 volts;
and the rectifier bridge is respectively connected with the friction nano generator and the plasma module and is used for converting the alternating current into direct current.
5. The gas sensing device according to claim 1, wherein the metal oxide is zinc oxide, tin oxide, tungsten oxide, iron oxide, titanium oxide, copper oxide, indium oxide, cobalt oxide, vanadium oxide, chromium oxide, germanium oxide, manganese oxide, or zirconium oxide.
6. The gas sensing device according to claim 1, wherein the insulating substrate is made of silicon dioxide, silicon, glass or ceramic.
7. The gas sensing device according to claim 1, wherein the source electrode and the drain electrode are both Cr/Au.
8. The gas sensing device of claim 1, wherein the plasma module is a tungsten needle having a radius of curvature greater than 0.1 μ ι η and less than 500 μ ι η.
CN202110219193.XA 2021-02-26 2021-02-26 Gas sensing device Active CN113447530B (en)

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Publication number Priority date Publication date Assignee Title
JP4659295B2 (en) * 2001-08-27 2011-03-30 ウチヤ・サーモスタット株式会社 Metal oxide semiconductor gas sensor
CN102778481B (en) * 2011-05-09 2014-06-11 中国科学院微电子研究所 Induction grid type amorphous metal oxide TFT gas sensor
KR20170041506A (en) * 2015-10-07 2017-04-17 전자부품연구원 Method for manufacturing a micro gas sensor
CN109187730B (en) * 2018-08-27 2020-10-20 河南大学 Self-driven CO2 sensor based on friction nano generator gas discharge
CN111610234B (en) * 2020-07-07 2021-09-07 上海大学 Acetone gas sensor of field effect transistor and preparation method thereof
CN112221344B (en) * 2020-09-03 2021-07-16 河南大学 CO (carbon monoxide)2Catalytic reduction apparatus and method

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