CN114740065A - MEMS residual chlorine electrode for detecting tap water - Google Patents

MEMS residual chlorine electrode for detecting tap water Download PDF

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CN114740065A
CN114740065A CN202210259067.1A CN202210259067A CN114740065A CN 114740065 A CN114740065 A CN 114740065A CN 202210259067 A CN202210259067 A CN 202210259067A CN 114740065 A CN114740065 A CN 114740065A
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electrode
measuring
wafer
residual chlorine
layer
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CN114740065B (en
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龚伟华
王磊
张猛
曹虎辰
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Hangzhou Kemis Iot Sensing Technology Co ltd
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    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28Electrolytic cell components
    • G01N27/30Electrodes, e.g. test electrodes; Half-cells
    • G01N27/301Reference electrodes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/406Cells and probes with solid electrolytes
    • G01N27/407Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4073Composition or fabrication of the solid electrolyte
    • G01N27/4074Composition or fabrication of the solid electrolyte for detection of gases other than oxygen
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/406Cells and probes with solid electrolytes
    • G01N27/407Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4077Means for protecting the electrolyte or the electrodes
    • GPHYSICS
    • G01MEASURING; TESTING
    • G01NINVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403Cells and electrode assemblies
    • G01N27/406Cells and probes with solid electrolytes
    • G01N27/407Cells and probes with solid electrolytes for investigating or analysing gases
    • G01N27/4078Means for sealing the sensor element in a housing

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Abstract

The invention provides an MEMS residual chlorine electrode for detecting tap water, and aims to solve the problem of low integration level of a counter electrode, a measuring electrode and a reference electrode of a residual chlorine detection sensor in the prior art. The MEMS residual chlorine electrode comprises a wafer, a counter electrode, a measuring electrode, a reference electrode and a silicon cover plate packaging layer; a counter electrode, a measuring electrode and a reference electrode are arranged on the wafer, and three gold conductive wires are etched on the wafer; the silicon cover plate packaging layer is arranged on the wafer; the measuring electrode is covered with a fluorinated ethylene propylene diaphragm, and the reference electrode is covered with an ion conduction layer; the counter electrode and the measuring electrode both comprise a gold layer and a platinum layer. The counter electrode, the measuring electrode and the reference electrode are integrated on the same wafer substrate, so that the integrated degree is high, the volume is small, and the counter electrode, the measuring electrode and the reference electrode are convenient to install when a circuit board is manufactured; the measurement electrode is covered with the fluorinated ethylene propylene membrane, so that the stability of detection data can be improved, the drift of the detection data is reduced, and the polarization of the electrode can be prevented.

Description

MEMS residual chlorine electrode for detecting tap water
Technical Field
The invention belongs to the technical field of detection of residual chlorine in domestic water, and particularly relates to an MEMS residual chlorine electrode for detecting tap water.
Background
MEMS sensors refer to microelectromechanical systems; the residual chlorine of the domestic tap water can be detected by adopting the residual chlorine detection sensor, so that whether the domestic tap water reaches the standard or not can be judged; the existing residual chlorine detection sensor comprises three electrodes, namely a counter electrode, a measuring electrode and a reference electrode, but the existing residual chlorine detection sensor has the problem of low integration level due to the fact that the three detection electrodes are separately arranged, and the volume of the residual chlorine detection sensor is large; in addition, the measurement data of the existing residual chlorine detection sensor has the problems of poor stability and easy drift.
Disclosure of Invention
The invention provides an MEMS residual chlorine electrode for detecting tap water, and aims to solve the problem that the integration level of a counter electrode, a measuring electrode and a reference electrode of a residual chlorine detection sensor in the prior art is low.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: an MEMS residual chlorine electrode for detecting tap water comprises a wafer, a counter electrode, a measuring electrode, a reference electrode and a silicon cover plate packaging layer; the wafer is provided with a counter electrode, a measuring electrode and a reference electrode, and three gold conducting wires which are connected with the counter electrode, the measuring electrode and the reference electrode one by one are etched on the wafer; the measuring electrode is a circular electrode, the counter electrode is an annular electrode arranged around the measuring electrode, and an annular gap is formed between the measuring electrode and the counter electrode; the silicon cover plate packaging layer is arranged on the wafer, and a reference electrode hole for exposing the reference electrode, a measuring electrode hole for exposing the measuring electrode and a counter electrode hole for exposing the counter electrode are formed in the silicon cover plate packaging layer; the measuring electrode is covered with a fluorinated ethylene propylene diaphragm, and the reference electrode is covered with an ion conduction layer; the counter electrode and the measuring electrode respectively comprise a gold layer arranged on the wafer and a platinum layer arranged on the gold layer.
The further improved scheme is as follows: the diameter of the measuring electrode is 2 mm; the area ratio of the measuring electrode to the counter electrode was 1.5: 1.
Based on the scheme, the diameter of the measuring electrode is 2mm, and the area ratio of the measuring electrode to the counter electrode is 1.5:1, so that the detection data are more accurate.
The further improved scheme is as follows: the thickness of the gold layer is 20nm, and the thickness of the platinum layer is 50 nm.
The further improved scheme is as follows: the wafer substrate is square, the counter electrode and the measuring electrode are positioned on the left half side of the wafer substrate, and the reference electrode is positioned on the right half side of the wafer substrate; the gold conducting wire for connecting the reference electrode is transversely arranged between the right boundary of the reference electrode and the wafer substrate, the gold conducting wire for connecting the counter electrode is longitudinally arranged between the gold layer of the counter electrode and the rear boundary of the wafer substrate, and the gold conducting wire for connecting the measuring electrode is longitudinally arranged between the gold layer of the measuring electrode and the rear boundary of the wafer substrate.
The further improved scheme is as follows: the reference electrode is a silver electrode or a silver chloride electrode.
The further improved scheme is as follows: the thickness of the reference electrode was 50 nm.
The further improved scheme is as follows: the length of the wafer substrate is 12mm, the width of the wafer substrate is 6mm, and the thickness of the wafer substrate is 1 mm.
The further improved scheme is as follows: the ion conduction layer is conductive epoxy glue, and the thickness of conductive epoxy glue is 200 um.
The beneficial effects of the invention are as follows:
the counter electrode, the measuring electrode and the reference electrode are integrated on the same wafer substrate, so that the integrated degree is high, the volume is small, and the counter electrode, the measuring electrode and the reference electrode are convenient to install when a circuit board is manufactured; in addition, the wafer substrate comprises a wafer at the bottom and a gold layer on the upper layer, the gold layer has good conductivity and good inertia, and the connection of the counter electrode, the measuring electrode and the reference electrode with an external circuit can be realized by etching three gold conductive wires on the wafer; the silicon cover plate packaging layer (silicon nitride layer) plays a role of insulation; the measurement electrode is covered with the fluorinated ethylene propylene membrane, so that the stability of detection data can be improved, the drift of the detection data can be reduced, and the polarization of the electrode can be prevented; the platinum layer can be used for testing the change of voltage in water; the ion conduction layer can protect the reference electrode on the premise of ensuring the normal interaction of ions
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and it will be apparent to those skilled in the art that other relevant drawings can be obtained from the drawings without inventive effort.
FIG. 1 is a schematic diagram of the structure of the MEMS residual chlorine electrode of the present invention.
FIG. 2 is a schematic diagram of the exploded structure of the MEMS residual chlorine electrode of the present invention.
The reference numbers in the figures illustrate:
1-a wafer; 2-a counter electrode; 3-a measuring electrode; 4-a reference electrode; 5-a silicon cover plate packaging layer; 6-an ion conducting layer; 7-fluorinated ethylene propylene membrane; 8-gold conductive wire.
Detailed Description
The technical solution 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. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the invention without inventive step, are within the scope of the invention.
Referring to fig. 1 and 2, an MEMS chlorine residual electrode for detecting tap water includes a wafer 1, a counter electrode 2, a measuring electrode 3, a reference electrode 4, and a silicon cover plate encapsulation layer 5; the wafer 1 is provided with a counter electrode 2, a measuring electrode 3 and a reference electrode 4, and three gold conducting wires 8 which are connected with the counter electrode 2, the measuring electrode 3 and the reference electrode 4 one by one are etched on the wafer 1; the measuring electrode 3 is a circular electrode, the counter electrode 2 is an annular electrode arranged around the measuring electrode 3, and an annular gap is arranged between the measuring electrode 3 and the counter electrode 2; the silicon cover plate packaging layer 5 is arranged on the wafer 1, and a reference electrode hole for exposing the reference electrode 4, a measuring electrode hole for exposing the measuring electrode 3 and a counter electrode hole for exposing the counter electrode 2 are formed in the silicon cover plate packaging layer 5; the measuring electrode 3 is covered with a fluorinated ethylene propylene diaphragm 7, and the reference electrode 4 is covered with an ion conduction layer 6; the counter electrode 2 and the measuring electrode 3 both comprise a gold layer arranged on the wafer 1 and a platinum layer arranged on the gold layer.
On the basis of the scheme, the diameter of the measuring electrode 3 is 2 mm; the area ratio of the measuring electrode 3 to the counter electrode 2 was 1.5: 1. The diameter of the measuring electrode 3 is 2mm, and the area ratio of the measuring electrode 3 to the counter electrode 2 is 1.5:1, so that the detection data is more accurate; tables 1 to 3 were obtained from actual measurement data;
table 1 shows the error values with respect to the standard solution when the area ratio of the measuring electrode 3 to the counter electrode 2 is 1 and the diameters of the measuring electrode 3 are 1.5mm, 2mm, 2.5mm and 3mm, respectively.
TABLE 1
Figure BDA0003550007290000041
Table 2 shows the error values with respect to the standard solution when the area ratio of the measuring electrode 3 to the counter electrode 2 was 1.5 and the diameters of the measuring electrode 3 were 1.5mm, 2mm, 2.5mm and 3mm, respectively.
TABLE 2
Figure BDA0003550007290000042
Table 3 shows the error values with respect to the standard solution when the area ratio of the measuring electrode 3 to the counter electrode 2 was 2 and the diameters of the measuring electrode 3 were 1.5mm, 2mm, 2.5mm and 3mm, respectively.
TABLE 3
Figure BDA0003550007290000051
As can be seen from tables 1 to 3, when the diameter of the measuring electrode 3 is 2mm and the area ratio of the measuring electrode 3 to the counter electrode 2 is 1.5:1, the error of the detection data is minimized and the detection effect is optimized.
On the basis of any scheme, the thickness of the gold layer is 20nm, and the thickness of the platinum layer is 50 nm.
On the basis of any scheme, the wafer 1 substrate is square, the counter electrode 2 and the measuring electrode 3 are positioned on the left half side of the wafer 1 substrate, and the reference electrode 4 is positioned on the right half side of the wafer 1 substrate; the gold conducting wire 8 for connecting the reference electrode 4 is transversely arranged between the reference electrode 4 and the right boundary of the wafer 1 substrate, the gold conducting wire 8 for connecting the counter electrode 2 is longitudinally arranged between the gold layer of the counter electrode 2 and the rear boundary of the wafer 1 substrate, and the gold conducting wire 8 for connecting the measuring electrode 3 is longitudinally arranged between the gold layer of the measuring electrode 3 and the rear boundary of the wafer 1 substrate.
On the basis of any scheme, the reference electrode 4 is a silver electrode or a silver chloride electrode.
On the basis of any of the above schemes, the thickness of the reference electrode 4 is 50 nm.
On the basis of any scheme, the length of the substrate of the wafer 1 is 12mm, the width of the substrate of the wafer is 6mm, and the thickness of the wafer is 1 mm.
On the basis of any one of the above schemes, the ion conduction layer is conductive epoxy glue, and the thickness of the conductive epoxy glue is 200 um.
The manufacturing process of the MEMS residual chlorine electrode comprises the following steps:
s100, sputtering a gold layer with the thickness of 20nm on the round crystal at the positions corresponding to the measuring electrode 3, the counter electrode 2 and the three gold conducting wires 8;
s200, sputtering platinum layers with the thickness of 50nm on the gold layers of the measuring electrode 3 and the counter electrode 2;
s300, electroplating silver/silver chloride with the thickness of 50nm on the reference electrode 4 in a sputtering mode;
s400, a silicon cover plate packaging layer 5 (a silicon nitride layer) is arranged on the upper portion of the wafer, and the reference electrode 4, the measuring electrode 3 and the counter electrode 2 are leaked out;
s500, a layer of fluorinated ethylene propylene membrane 7 is covered on the measuring electrode 3 and the counter electrode 2, and an ion conducting layer 6 is covered on the reference electrode 4.
The invention is not limited to the above alternative embodiments, and any other various forms of products can be obtained by anyone in the light of the present invention, but any changes in shape or structure thereof, which fall within the scope of the present invention as defined in the claims, fall within the scope of the present invention.

Claims (8)

1. An MEMS residual chlorine electrode for detecting tap water is characterized by comprising a wafer, a counter electrode, a measuring electrode, a reference electrode and a silicon cover plate packaging layer; the wafer is provided with a counter electrode, a measuring electrode and a reference electrode, and three gold conducting wires which are connected with the counter electrode, the measuring electrode and the reference electrode one by one are etched on the wafer; the measuring electrode is a circular electrode, the counter electrode is an annular electrode arranged around the measuring electrode, and an annular gap is formed between the measuring electrode and the counter electrode; the silicon cover plate packaging layer is arranged on the wafer, and a reference electrode hole for exposing the reference electrode, a measuring electrode hole for exposing the measuring electrode and a counter electrode hole for exposing the counter electrode are formed in the silicon cover plate packaging layer; the measuring electrode is covered with a fluorinated ethylene propylene diaphragm, and the reference electrode is covered with an ion conduction layer; the counter electrode and the measuring electrode respectively comprise a gold layer arranged on the wafer and a platinum layer arranged on the gold layer.
2. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 1, wherein: the diameter of the measuring electrode is 2 mm; the area ratio of the measuring electrode to the counter electrode was 1.5: 1.
3. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 1, wherein: the thickness of the gold layer is 20nm, and the thickness of the platinum gold layer is 50 nm.
4. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 1 or 3, wherein: the wafer substrate is square, the counter electrode and the measuring electrode are positioned on the left half side of the wafer substrate, and the reference electrode is positioned on the right half side of the wafer substrate; the gold conducting wire for connecting the reference electrode is transversely arranged between the right boundary of the reference electrode and the wafer substrate, the gold conducting wire for connecting the counter electrode is longitudinally arranged between the gold layer of the counter electrode and the rear boundary of the wafer substrate, and the gold conducting wire for connecting the measuring electrode is longitudinally arranged between the gold layer of the measuring electrode and the rear boundary of the wafer substrate.
5. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 1, wherein: the reference electrode is a silver electrode or a silver chloride electrode.
6. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 5, wherein: the thickness of the reference electrode was 50 nm.
7. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 1, wherein: the length of the wafer substrate is 12mm, the width of the wafer substrate is 6mm, and the thickness of the wafer substrate is 1 mm.
8. The MEMS residual chlorine electrode for detecting tap water as claimed in claim 1, wherein: the ion conduction layer is conductive epoxy glue, and the thickness of conductive epoxy glue is 200 um.
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Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2001281200A (en) * 2000-03-31 2001-10-10 Akifumi Yamada Measuring electrode for free residual chlorine and measuring method using it
US20030106810A1 (en) * 1996-06-17 2003-06-12 Douglas Joel S. Electrochemical test device and related methods
JP2005274226A (en) * 2004-03-23 2005-10-06 Akifumi Yamada Free residual chlorine concentration measuring instrument and free residual chlorine measuring method
US20070114137A1 (en) * 2005-11-22 2007-05-24 Satoshi Nomura Residual chlorine measuring method and residual chlorine measuring device
US20090278556A1 (en) * 2006-01-26 2009-11-12 Nanoselect, Inc. Carbon Nanostructure Electrode Based Sensors: Devices, Processes and Uses Thereof
KR20130117515A (en) * 2012-04-18 2013-10-28 대윤계기산업 주식회사 Electrochemical gas permeable membrane type free residual chlorine sensor
CN105628757A (en) * 2015-12-30 2016-06-01 中国科学院电子学研究所 ORP sensing chip based on MEMS and manufacturing method of ORP sensing chip
CN212228800U (en) * 2020-04-02 2020-12-25 郑州炜盛电子科技有限公司 Diaphragm type residual chlorine sensor
CN215415193U (en) * 2021-07-27 2022-01-04 江苏集萃分子工程研究院有限公司 Electrochemical detection device and electrode chip thereof

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20030106810A1 (en) * 1996-06-17 2003-06-12 Douglas Joel S. Electrochemical test device and related methods
JP2001281200A (en) * 2000-03-31 2001-10-10 Akifumi Yamada Measuring electrode for free residual chlorine and measuring method using it
JP2005274226A (en) * 2004-03-23 2005-10-06 Akifumi Yamada Free residual chlorine concentration measuring instrument and free residual chlorine measuring method
US20070114137A1 (en) * 2005-11-22 2007-05-24 Satoshi Nomura Residual chlorine measuring method and residual chlorine measuring device
US20090278556A1 (en) * 2006-01-26 2009-11-12 Nanoselect, Inc. Carbon Nanostructure Electrode Based Sensors: Devices, Processes and Uses Thereof
KR20130117515A (en) * 2012-04-18 2013-10-28 대윤계기산업 주식회사 Electrochemical gas permeable membrane type free residual chlorine sensor
CN105628757A (en) * 2015-12-30 2016-06-01 中国科学院电子学研究所 ORP sensing chip based on MEMS and manufacturing method of ORP sensing chip
CN212228800U (en) * 2020-04-02 2020-12-25 郑州炜盛电子科技有限公司 Diaphragm type residual chlorine sensor
CN215415193U (en) * 2021-07-27 2022-01-04 江苏集萃分子工程研究院有限公司 Electrochemical detection device and electrode chip thereof

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