CN210109021U - Integrated micro-nano sensor - Google Patents
Integrated micro-nano sensor Download PDFInfo
- Publication number
- CN210109021U CN210109021U CN201920163455.3U CN201920163455U CN210109021U CN 210109021 U CN210109021 U CN 210109021U CN 201920163455 U CN201920163455 U CN 201920163455U CN 210109021 U CN210109021 U CN 210109021U
- Authority
- CN
- China
- Prior art keywords
- sensor
- platinum
- silicon substrate
- electrode
- iridium
- 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.)
- Withdrawn - After Issue
Links
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 108
- 239000000758 substrate Substances 0.000 claims abstract description 88
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 56
- 239000010703 silicon Substances 0.000 claims abstract description 56
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 43
- 239000011521 glass Substances 0.000 claims abstract description 41
- 239000007788 liquid Substances 0.000 claims abstract description 39
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 33
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 26
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910000457 iridium oxide Inorganic materials 0.000 claims abstract description 26
- 238000003860 storage Methods 0.000 claims abstract description 24
- 229910021607 Silver chloride Inorganic materials 0.000 claims abstract description 19
- 229910052709 silver Inorganic materials 0.000 claims abstract description 19
- 239000004332 silver Substances 0.000 claims abstract description 19
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000002347 injection Methods 0.000 claims abstract description 18
- 239000007924 injection Substances 0.000 claims abstract description 18
- 239000001103 potassium chloride Substances 0.000 claims abstract description 16
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 16
- 239000012047 saturated solution Substances 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000565 sealant Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 24
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000005342 ion exchange Methods 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- UUWCBFKLGFQDME-UHFFFAOYSA-N platinum titanium Chemical compound [Ti].[Pt] UUWCBFKLGFQDME-UHFFFAOYSA-N 0.000 claims description 7
- 239000004593 Epoxy Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 4
- 239000002090 nanochannel Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000001039 wet etching Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 8
- 230000002035 prolonged effect Effects 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 229910052814 silicon oxide Inorganic materials 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005672 electromagnetic field Effects 0.000 description 3
- 238000004080 punching Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002596 correlated effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical group [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- 238000000347 anisotropic wet etching Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000005459 micromachining Methods 0.000 description 1
- 239000002991 molded plastic Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001259 photo etching Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000005297 pyrex Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Landscapes
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
The integrated micro-nano sensor comprises a silicon substrate (14) and a glass substrate (10) which are bonded together, wherein the silicon substrate (14) is respectively provided with a temperature sensor (1), a pH sensor (2) and a conductivity sensor (3), the pH sensor (2) comprises an iridium/iridium oxide working electrode (5) and a platinum counter electrode (6) which are arranged in an inner circular ring and an outer circular ring, a downward opening cavity is arranged at the bottom of the silicon substrate, a potassium chloride saturated solution storage cavity (12) is formed by the silicon substrate and the glass substrate (10), and the top wall of the storage cavity (12) is provided with a nano-scale tapered micropore (9) array channel; the glass substrate (10) is provided with a liquid injection hole (13) for preparing sealant; a platinum electrode lead (11) is arranged on the upper surface of the glass substrate (10), and a silver/silver chloride reference electrode layer (7) is arranged at the tail end of the platinum electrode lead; three parameters of the same site of the water environment can be measured.
Description
Technical Field
The utility model relates to an integrated micro-nano sensor that is used for water pH value, conductivity and the quick on-line measuring of temperature three parameters such as ocean, rivers, lakes, reservoir belongs to environmental protection technical field, also belongs to sensor technical field.
Background
The pH value, the conductivity and the temperature are basic parameters for representing the quality of the water environment, and are necessary indexes for controlling the quality of environmental water bodies, household drinking water and ocean water bodies. The three parameters are correlated and influence each other, so that the measurement must be performed at the same time and at the same time at the same point to meet the requirement of preparing the measurement. The conventional pH is measured by adopting a glass electrode and an electrochemical method, and the response time is longer; the conductivity is measured by adopting double electrodes, the temperature is measured by adopting a platinum resistor, the three sensors mainly measure in a discrete mode, and parts of the three sensors are packaged together in an integrated mode to measure.
In a commonly used three-electrode system for electrochemically measuring the pH value, a glassy carbon electrode is adopted as a working electrode, an Ag/AgCl electrode is adopted as a reference electrode, and a platinum electrode is adopted as a counter electrode. The system is mainly three independent large electrodes, can not be integrated with other electrodes to be prepared on a sensor chip, the distance and the relative area between a working electrode and a counter electrode are difficult to control, and the measurement accuracy is influenced. A micro Ag/AgCl all-solid-state reference electrode is developed based on a micro-nano manufacturing technology, but the storage time of a potassium chloride saturated solution required by the electrode on the surface of the electrode is short, so that the service life of the electrode is short, and the requirement of long-time continuous working of a sensor cannot be met.
The applicant of the present application filed an invention patent application entitled "silver/silver chloride reference electrode and a manufacturing method thereof" on 29/11/2017, published on 20/04/2018, and the document number is CN107941876A, and provides an Ag/AgCl reference electrode and a manufacturing method thereof, which are remarkably characterized in that a microstructure of a tapered micropore array is integrated, so that the function of ion exchange can be achieved, the speed of ion exchange can be effectively reduced, and the stability and the service life of the electrode can be greatly improved. The utility model discloses can regard as the further research and development achievement on this technical basis.
Disclosure of Invention
The utility model aims to solve the technical problem that a three parameter fast on-line measuring's integrated micro-nano sensor of pH value, conductivity and temperature that is used for same position point of water such as ocean, rivers, lakes, reservoirs and time point is provided, overcome the shortcoming of current sensor, the integrated degree of sensor is high, long service life, stability is good.
In order to solve the technical problem, the utility model discloses receive the technical scheme that the sensor adopted a little and do:
an integrated micro-nano sensor for rapidly detecting three parameters of pH value, conductivity and temperature of a water body on line comprises a Pyrex7740 glass substrate (10) which can be bonded with a silicon chip, wherein a silicon substrate (14) with a crystal face (100) on the surface and polished and oxidized on two sides is covered on the glass substrate (10) in a bonding mode, and the glass substrate and the silicon substrate are bonded into a whole; the sensor is characterized in that a temperature sensor (1), a pH value sensor (2) and a conductivity sensor (3) are respectively arranged on a silicon substrate (14), the temperature sensor (1) is a platinum wire thermistor (15) arranged on the surface of the silicon substrate (14), and the conductivity sensor (3) is 2 pairs of platinum electrodes (16) arranged on the surface of the silicon substrate (14); the pH value sensor (2) comprises an iridium/iridium oxide working electrode (5) and a platinum counter electrode (6) which are arranged on the surface of a silicon substrate (14) and respectively form an inner ring and an outer ring, a downward opening cavity is arranged below the iridium/iridium oxide working electrode (5) positioned on the inner ring, the opening cavity and the glass substrate (10) form a liquid storage cavity (12) for storing potassium chloride saturated solution, the top wall of the liquid storage cavity (12) is provided with a plurality of nanoscale conical micropores (9) etched by wet etching and having large outer wall pore diameter and small inner wall pore diameter, an array of conical micropores (9) positioned in the inner ring of the iridium/iridium oxide working electrode (5) is formed, and each conical micropore (9) is used as a nano channel which is contacted with an external object to be measured to carry out ion exchange between the two sides; the glass substrate (10) is provided with a liquid injection hole (13) communicated with the liquid storage cavity (12) and is provided with a sealant for packaging the liquid injection hole (13), and a potassium chloride saturated solution injected through the liquid injection hole (13) is stored in the liquid storage cavity (12); a platinum electrode lead (11) is arranged on the upper surface of the glass substrate (10) and is communicated with the liquid storage cavity (12), and a silver/silver chloride reference electrode layer (7) is arranged on the upper surface of the tail end section of the platinum electrode lead (11).
The following is the further scheme of the micro-nano sensor:
the iridium/iridium oxide working electrode (5) of the pH value sensor (2) is a micron-sized electroplated layer formed on a nanometer-sized platinum thin layer with the thickness of nanometer and the width of millimeter, which is formed by a Lift-off process, and the platinum counter electrode (6), the temperature sensor (1) and the conductivity sensor (3) are platinum thin layers which are directly formed by the Lift-off process and have the thickness of nanometer and the width of micron.
The iridium/iridium oxide working electrode (5) is a closed ring, and a working electrode lead-out wire of the iridium/iridium oxide working electrode (5) is led out from a ring body of the iridium/iridium oxide working electrode to a terminal on one side of the silicon substrate (14); the platinum counter electrode (6) is an open circular ring, and the platinum counter electrode (6) is led out from 2 open ends of the open circular ring to a terminal on the same side of the silicon substrate (14).
The temperature sensor (1), the pH value sensor (2) and the conductivity sensor (3) are arranged in parallel, the pH value sensor (2) and the conductivity sensor (3) are located in the middle, and the temperature sensor (1) and the conductivity sensor (3) are respectively located on the left side and the right side of the pH value sensor (2).
The whole section of the metal platinum wire of the temperature sensor (1) is repeatedly arranged back and forth in the area of the region where the whole section of the metal platinum wire is located, so that the resistance value is an integer critical value when the length and the width of the whole section of the metal platinum wire forming the temperature sensor (1) can reach the temperature of 0 ℃; the integral critical value is 1000 ohm or 5000 ohm or 10000 ohm.
The conductivity sensor (3) is designed into a double semicircular opposite structure.
The silver/silver chloride electrode layer sequentially comprises a titanium-platinum electrode substrate conducting layer, a metal silver layer and an Ag/AgCl layer formed by treating the metal silver layer with hydrochloric acid from the bottom to the surface.
The back of the glass substrate (10) is coated with an epoxy light shading layer.
The temperature sensor (1), the pH value sensor (2) and the conductivity sensor (3) are arranged in the silicon substrate (14) in an externally-packaged mode, the regions are opened, other portions are completely packaged, and lead-out wires of all electrodes are led out.
Compared with the prior art, the pH/conductivity/temperature sensor integrates three sensors on a silicon-based chip, adopts micro-nano manufacturing technology to manufacture in batches, and has the advantages of simple process, good consistency and low manufacturing cost; three parameters of the same site of the water environment can be measured, and the three correlated parameters can be accurately measured; the three-parameter electrode is designed and distributed on the surface of the silicon wafer, and is convenient to clean by adopting a brush when in application; the pH sensor adopts a potassium chloride saturated solution pre-packaging mode, so that the stability of the sensor is improved, and the service life of the sensor is prolonged.
The utility model discloses pH/conductivity/temperature sensor is used for ion exchange's toper micropore (9) array, potassium chloride saturated solution stock solution chamber (12), Ag AgCl electrode based on micro-machining technology preparation. Because the conical micropore (9) array not only has the function of ion exchange, but also has the nanometer aperture, the ion exchange rate is greatly reduced, the service time of a potassium chloride saturated solution can be effectively prolonged, the service life of a reference electrode of the potassium chloride saturated solution is obviously prolonged, and the service life of the micro-nano sensor is further obviously prolonged. The utility model discloses with the integrated manufacturing of each electrode, realize whole detection sensor's miniaturization, have longer life simultaneously, form a novel sensor microchip, but have the batchization preparation, reduce cost, uniformity are good etc. are showing advantages, provide support for receiving the application of sensor in the water quality monitoring field a little, have important practical application and worth.
Drawings
FIG. 1 is a schematic diagram of the overall structure of the micro-nano sensor of the utility model;
FIG. 2 is a schematic diagram of the sectional structure of the micro-nano sensor of the present invention;
FIG. 3 is a schematic view of an exposed surface of a silicon substrate;
FIG. 4 is a schematic view of a bonding surface of a silicon substrate;
FIG. 5 is a schematic view of a bonding surface of a glass substrate;
FIG. 6 is a schematic bottom view of a glass substrate;
FIG. 7 is a schematic cross-sectional view showing the shape change at each step in the process of manufacturing a silicon substrate; wherein the content of the first and second substances,
FIG. 7-1 is a schematic view showing an initial state of silicon substrate fabrication;
FIG. 7-2 is a schematic view showing a state where a window of a silicon oxide layer is formed after spin coating a photoresist on both sides of a silicon substrate;
FIG. 7-3 is a schematic diagram showing the state of preparing a nano-scale tapered micro-pore array and a liquid storage chamber by KOH etching of a silicon substrate;
FIG. 7-4 is a schematic view showing a state of a platinum electrode conductive layer prepared by sputtering and a Lift-off process;
FIG. 7-5 is a schematic view showing a state where the iridium/iridium oxide working electrode (5) is plated and the remaining silicon oxide layer of the substrate is removed;
FIG. 8 is a schematic cross-sectional view showing the shape change of each step in the process of manufacturing a glass substrate; wherein the content of the first and second substances,
FIG. 8-1 is a schematic view showing a state where a liquid injection hole is formed in a glass substrate;
FIG. 8-2 is a schematic view showing a state in which a platinum electrode lead and a titanium-platinum electrode base conductive layer are formed on the surface of a glass substrate;
fig. 8-3 is a schematic view of a state where silver is electroplated on a titanium-platinum conductive layer and a silver/silver chloride reference electrode layer is formed.
Detailed Description
The present invention will be described in further detail with reference to the following embodiments.
The utility model is used for detect three quick on-line measuring's of aquatic pH value, conductivity and temperature integration micro-nano sensor, as shown in figure 1, figure 2, including can with silicon chip bonded Pyrex7740 glass substrate 10, glass substrate 10 upper surface covers with the mode rather than bonded has the silicon chip 14 that the surface is 100 crystal planes, two-sided polishing and oxidation, and the two bonds integratively. The silicon substrate 14 is respectively provided with a temperature sensor 1, a pH value sensor 2 and a conductivity sensor 3, and the temperature sensor 1 is a platinum wire thermistor 15 arranged on the surface of the silicon substrate 14. The conductivity sensor 3 is 2 pairs of platinum electrodes 16 disposed on the surface of the silicon substrate 14.
The pH value sensor 2 comprises an iridium/iridium oxide working electrode 5 and a platinum counter electrode 6 which are arranged on the surface of a silicon substrate 14 in an inner ring and an outer ring respectively; as shown in fig. 2 and 4, the pH sensor 2 further includes: a downward opening cavity is arranged below the iridium/iridium oxide working electrode 5 of the inner ring, the opening cavity and a glass substrate 10 form a liquid storage cavity 12 for storing potassium chloride saturated solution, the top wall of the liquid storage cavity 12 is provided with a plurality of nano-scale tapered micropores 9 which are etched by wet etching and have large outer wall apertures and small inner wall apertures, a tapered micropore 9 array which is arranged in the inner ring of the iridium/iridium oxide working electrode 5 is formed, and each tapered micropore 9 is used as a nano-channel which is contacted with an external object to be tested to carry out ion exchange between the two; as shown in fig. 5 and 6, the glass substrate 10 is provided with a liquid injection hole 13 communicated with the liquid storage chamber 12, and is provided with a sealant for sealing the liquid injection hole 13, and the liquid storage chamber 12 stores a potassium chloride saturated solution injected through the liquid injection hole 13; the upper surface of the glass substrate 10 is provided with a platinum electrode lead 11 which is communicated with the liquid storage cavity 12, and the upper surface of the end section of the platinum electrode lead 11 is provided with a silver/silver chloride reference electrode layer 7.
As shown in fig. 3, the iridium/iridium oxide working electrode 5 of the pH sensor 2 is a micron-sized plated layer on a nano-sized platinum thin layer 19 formed by a Lift-off process and having a width of a millimeter, and the platinum counter electrode 6, the temperature sensor 1, and the conductivity sensor 3 are nano-sized platinum thin layers directly formed by a Lift-off process and having a width of a micron.
As shown in fig. 1 and 3, the iridium/iridium oxide working electrode 5 is a closed ring, and the iridium/iridium oxide working electrode 5 leads out a working electrode lead-out wire from the ring body to a terminal on one side of the silicon substrate 14; the platinum counter electrode 6 is an open circular ring, and the platinum counter electrode 6 is led out from 2 open ends of the open circular ring to a terminal on the same side of the silicon substrate 14. The working electrode in the pH sensor is made of iridium/iridium oxide materials, the sensitivity is high, the response speed is high, the electrode is designed in a circular ring shape, the center of the circular ring is subjected to ion exchange with a reference electrode on the back through a nanopore array, the reference electrode is designed on the back of the working electrode, a KCl saturated solution storage solution is designed on the back, an Ag/AgCl electrode is manufactured on Pyrex glass, a Pt counter electrode and the working electrode are arranged on the outer ring of the working electrode in a concentric circle mode, and the environment electromagnetic field interference resistance of the device can be effectively improved through the circular ring shape design.
As shown in fig. 1 and 3, the temperature sensor 1, the pH sensor 2, and the conductivity sensor 3 are arranged in parallel on a centimeter-square silicon substrate 14, the pH sensor 2 and the conductivity sensor 3 are located in the middle, and the temperature sensor 1 and the conductivity sensor 3 are located on the left and right sides of the pH sensor 2, respectively. The layout can facilitate cleaning of dirt on the surface of the electrode by the electric brush in later use.
As shown in fig. 1 and fig. 3, the whole section of the platinum wire of the temperature sensor (1) is repeatedly arranged back and forth in the area where the platinum wire is located, so that the resistance value is an integer critical value when the length and the width of the whole section of the platinum wire forming the temperature sensor (1) can reach the temperature of 0 ℃; the integer critical value can be 1000 ohm or 5000 ohm or 10000 ohm. The platinum wire thermistor 15 is made of pure platinum metal with the material content of more than 99.99%, the resistance value is an integer critical value of 1000 ohm or 5000 ohm or 10000 ohm when the temperature is controlled to be 0 ℃ through the length, the width and the thickness, and the resistance of a lead wire part is less than 1 ohm; the corresponding platinum wire thermistors 15 may be referred to as 1000 platinum thermistors, 5000 platinum thermistors, and 10000 platinum thermistors, respectively. Of course, the larger the value of the integer critical value is, the higher the test precision is, but the difficulty of the system is also correspondingly improved. The conductivity sensor 3 is designed into a double semicircular opposite structure so as to improve the anti-interference capability of the electrode against the environmental electromagnetic field. The electrode plate of the conductivity sensor 3 is made of Pt material, corrosion resistance and stable performance are achieved, and the electrode plate with double semi-circular shapes is designed to be good due to the fact that the semi-circular arc-shaped concentric circles are adopted, so that the environment electromagnetic field interference resistance of the electrode is further improved.
As shown in fig. 2, the silver/silver chloride electrode layer sequentially comprises a titanium-platinum electrode substrate conductive layer, a metal silver layer and an Ag/AgCl layer formed by treating the metal silver layer with hydrochloric acid from bottom to surface. The back of the glass substrate 10 is coated with an epoxy matte layer.
The areas of the temperature sensor 1, the pH value sensor 2 and the conductivity sensor 3 on the silicon substrate 14 are opened, and other parts are completely packaged, and lead-out wires of all electrodes are led out. The outer package may be a metal shell, and if large, is more suitably an injection molded plastic part.
The utility model discloses receive sensor's preparation a little, include silicon substrate 14's preparation, glass substrate 10's preparation and the bonding of the two respectively, the injection of potassium chloride saturated solution still includes sealed gluey formation. The silicon substrate 14 is fabricated as shown in fig. 7, including the steps of:
step one, as shown in fig. 7-1, a silicon wafer with a single polished and oxidized surface of a 100 crystal face is selected as a material of a silicon substrate 14, the surface of the silicon substrate is provided with a silicon oxide layer 17, the thickness of the silicon oxide layer 17 is 2um, and the surface flatness of the silicon wafer is less than 1 um.
And step two, as shown in figure 7-2, spraying photoresist 18 on the two sides of the substrate, photoetching and developing, etching the silicon oxide layer by using BOE corrosive liquid, and preparing a window of the liquid storage cavity 12 and a nano channel window.
And step three, as shown in fig. 7-3, adopting 30% KOH corrosive liquid, etching the silicon layer by an anisotropic wet method at 50 ℃, preparing a liquid storage cavity 12 and an ion exchange channel until the front surface and the back surface are etched through, and controlling the size of the through hole to be less than 1um by controlling the etching rate and the etching time to form the tapered micropore 9 array.
And step four, as shown in fig. 7-4, preparing a platinum electrode conducting layer and a lead wire on a silicon wafer with a conical micropore 9 array by adopting sputtering and Lift-off processes, wherein the platinum electrode conducting layer comprises a platinum bottom layer of the iridium/iridium oxide working electrode 5 and a platinum counter electrode 6.
And step five, as shown in fig. 7-5, electroplating an iridium/iridium oxide working electrode 5 electroplated layer on the platinum bottom surface of the iridium/iridium oxide working electrode 5.
The glass substrate 10 is produced as shown in fig. 8, and includes the following steps:
step one, as shown in fig. 8-1, selecting a Pyrex7740 glass substrate 10 which can be bonded with a silicon chip, punching a liquid injection hole 13 with the diameter of 1mm to 2mm for injecting a potassium chloride saturated solution at a set position by adopting a laser punching method or an ultrasonic punching method, and configuring a sealant with the shape matched with the liquid injection hole 13.
Step two, as shown in fig. 8-2, a platinum electrode lead 11 and a titanium-platinum electrode base conductive layer are firstly prepared on the surface of the glass substrate 10 by lift-off process.
Step three, as shown in fig. 8-3, a layer of metallic silver is formed on the titanium-platinum conductive layer by electroplating silver, and a silver/silver chloride reference electrode layer 7 is formed after hydrochloric acid treatment.
The bonding of the silicon substrate 14 and the glass substrate 10 comprises aligning the prepared silicon substrate 14 with the glass substrate 10, bonding the silicon substrate 14 and the glass substrate 10 by a silicon-glass anodic bonding technology to form a complete plate-shaped sensor array body, and cutting a single sensor shown in fig. 1 and 2 along a designed cutting line by a silicon chip cutting machine. And (3) placing each micro-nano sensor in a state that the solution does not flow back, and injecting a saturated potassium chloride solution into the liquid storage cavity 12 through the liquid injection hole 13. And after the liquid is added, the sealant is extruded into the liquid injection hole 13, and then the micro-nano sensor is placed in an oven to dry and cure the sealant. The manufacturing of the glass substrate 10 further comprises spin-coating an epoxy light-shielding layer on the back surface of the glass substrate 10, wherein the epoxy light-shielding layer can be spin-coated after the liquid injection hole 13 is drilled. The epoxy light-shielding layer prevents the reference electrode from being influenced by illumination. And welding the lead of each electrode, and packaging according to the requirements. The measured value is obtained through the reading circuit, and then the back end circuit is matched for actual test.
The utility model discloses a sensor signal reads out method and parameter calibration method:
(1) the temperature sensor measures resistance change of the Pt wire along with temperature change by adopting a Wheatstone bridge method, the temperature and the resistance have a linear relation, and a temperature value is obtained through the measured resistance value;
(2) the conductivity sensor is tested by loading 1kHz alternating signals, and is calibrated with temperature parameters to obtain a conductivity value;
(3) the pH sensor measures the potential difference between the working electrode and the reference electrode according to an electrochemical three-electrode system, the pH value and the potential difference are in a linear relation, and the pH value and the temperature parameter are calibrated to obtain the final pH value.
The utility model relates to a structural design and overall arrangement of three sensor have as follows and show the advantage:
(1) the three sensors are integrated on the same microchip, can measure and measure the environmental parameters of the same locus at the same time, is beneficial to back-end data analysis and parameter calibration, and improves the accuracy of measurement.
(2) The preparation process of the three sensors is compatible with a Micro Electro Mechanical System (MEMS) process, so that large-scale batch preparation can be realized, and the manufacturing cost of a single device is reduced. The Pt resistance wire of the temperature sensor, the 4 Pt electrodes of the conductivity sensor, the Pt counter electrode of the pH sensor and the electrode leads of all the electrodes are completed on the (100) silicon substrate 14 by adopting a metal sputtering and stripping process (Lift-off), the nanopore array and the liquid storage tank are completed by adopting a potassium hydroxide anisotropic wet etching process, and the Ag/AgCl electrode is completed on a Pyrex7740 slide by adopting metal sputtering, Lift-off and hydrochloric acid treatment. The whole process preparation flow is compatible with a Micro Electro Mechanical System (MEMS) process, and batch manufacturing of dozens to hundreds of devices can be carried out on a 4-inch or 8-inch MEMS manufacturing platform.
(3) The reference electrode in the pH sensor is stored in a potassium chloride saturated solution, and ion exchange is carried out through the nano-pores, so that the requirement of ion exchange is met, the ion exchange rate is effectively reduced, the service life of the reference electrode is obviously prolonged, and the service life of the whole sensor is also prolonged.
The utility model discloses receive sensor a little can be used for three quick on-line measuring of parameters of aquatic pH value, conductivity and temperature such as ocean, rivers, lake, reservoir. The using method is the same as the existing online detection method.
Claims (9)
1. An integrated micro-nano sensor is used for rapidly detecting three parameters of pH value, conductivity and temperature of a water body on line, and comprises a Pyrex7740 glass substrate (10) which can be bonded with a silicon substrate, wherein the upper surface of the glass substrate (10) is covered with the silicon substrate (14) which has a crystal face with a surface of (100) and is polished and oxidized on two sides in a bonding mode, and the glass substrate and the silicon substrate are bonded into a whole; the sensor is characterized in that a temperature sensor (1), a pH value sensor (2) and a conductivity sensor (3) are respectively arranged on a silicon substrate (14), the temperature sensor (1) is a platinum wire thermistor (15) arranged on the surface of the silicon substrate (14), and the conductivity sensor (3) is 2 pairs of platinum electrodes (16) arranged on the surface of the silicon substrate (14); the pH value sensor (2) comprises an iridium/iridium oxide working electrode (5) and a platinum counter electrode (6) which are arranged on the surface of a silicon substrate (14) and respectively form an inner ring and an outer ring, a downward opening cavity is arranged below the iridium/iridium oxide working electrode (5) positioned on the inner ring, the opening cavity and the glass substrate (10) form a liquid storage cavity (12) for storing potassium chloride saturated solution, the top wall of the liquid storage cavity (12) is provided with a plurality of nanoscale conical micropores (9) etched by wet etching and having large outer wall pore diameter and small inner wall pore diameter, an array of conical micropores (9) positioned in the inner ring of the iridium/iridium oxide working electrode (5) is formed, and each conical micropore (9) is used as a nano channel which is contacted with an external object to be measured to carry out ion exchange between the two sides; the glass substrate (10) is provided with a liquid injection hole (13) communicated with the liquid storage cavity (12) and is provided with a sealant for packaging the liquid injection hole (13), and a potassium chloride saturated solution injected through the liquid injection hole (13) is stored in the liquid storage cavity (12); a platinum electrode lead (11) is arranged on the upper surface of the glass substrate (10) and is communicated with the liquid storage cavity (12), and a silver/silver chloride reference electrode layer (7) is arranged on the upper surface of the tail end section of the platinum electrode lead (11).
2. An integrated micro-nano sensor according to claim 1, wherein the iridium/iridium oxide working electrode (5) of the pH sensor (2) is a micron-sized electroplated layer on a nanometer-sized platinum thin layer with a millimeter-sized width formed by a Lift-off process, and the platinum counter electrode (6), the temperature sensor (1) and the conductivity sensor (3) are nanometer-sized platinum thin layers with a micron-sized width directly formed by a Lift-off process.
3. The integrated micro-nano sensor according to claim 1, wherein the iridium/iridium oxide working electrode (5) is a closed ring, and a working electrode lead-out wire of the iridium/iridium oxide working electrode (5) is led out from the ring body of the iridium/iridium oxide working electrode to a terminal on one side of the silicon substrate (14); the platinum counter electrode (6) is an open circular ring, and the platinum counter electrode (6) is led out from 2 open ends of the open circular ring to a terminal on the same side of the silicon substrate (14).
4. The integrated micro-nano sensor according to claim 1, wherein the temperature sensor (1), the pH sensor (2) and the conductivity sensor (3) are arranged in parallel, the pH sensor (2) and the conductivity sensor (3) are located in the middle, and the temperature sensor (1) and the conductivity sensor (3) are respectively located at the left side and the right side of the pH sensor (2).
5. The integrated micro-nano sensor according to claim 1, wherein the whole section of the metal platinum wire of the platinum wire thermistor (15) as the temperature sensor (1) is repeatedly arranged back and forth in the area where the whole section of the metal platinum wire is located, so that the resistance value is an integer critical value when the length and the width of the whole section of the metal platinum wire forming the temperature sensor (1) can reach the temperature of 0 ℃; the integral critical value is 1000 ohm or 5000 ohm or 10000 ohm.
6. An integrated micro-nano sensor according to claim 1, characterized in that the conductivity sensor (3) is designed as a double semicircular counter structure.
7. The micro-nano sensor according to claim 1, wherein the silver/silver chloride electrode layer comprises a titanium-platinum electrode substrate conducting layer, a metal silver layer and an Ag/AgCl layer formed by treating the metal silver layer with hydrochloric acid in sequence from bottom to surface.
8. A micro-nano sensor according to claim 1, wherein the back of the glass substrate (10) is coated with an epoxy light shielding layer.
9. A micro-nano sensor according to claim 1, comprising an outer package, wherein the outer package is provided with openings in areas where the temperature sensor (1), the pH sensor (2) and the conductivity sensor (3) are located on the silicon substrate (14), and other parts are all packaged, and lead-out wires of the electrodes are led out.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920163455.3U CN210109021U (en) | 2019-01-30 | 2019-01-30 | Integrated micro-nano sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201920163455.3U CN210109021U (en) | 2019-01-30 | 2019-01-30 | Integrated micro-nano sensor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN210109021U true CN210109021U (en) | 2020-02-21 |
Family
ID=69530743
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201920163455.3U Withdrawn - After Issue CN210109021U (en) | 2019-01-30 | 2019-01-30 | Integrated micro-nano sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN210109021U (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109813778A (en) * | 2019-01-30 | 2019-05-28 | 宁波大学 | A kind of integrated micro-nano sensor and preparation method thereof |
-
2019
- 2019-01-30 CN CN201920163455.3U patent/CN210109021U/en not_active Withdrawn - After Issue
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109813778A (en) * | 2019-01-30 | 2019-05-28 | 宁波大学 | A kind of integrated micro-nano sensor and preparation method thereof |
| CN109813778B (en) * | 2019-01-30 | 2023-11-21 | 宁波大学 | Integrated micro-nano sensor and manufacturing method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109813778B (en) | Integrated micro-nano sensor and manufacturing method thereof | |
| EP2363705B1 (en) | Microfabricated liquid-junction reference electrode | |
| US8784640B2 (en) | Amperometric electrochemical sensor and method for manufacturing same | |
| CN108680627B (en) | Micro-nano sensor for detecting organic matter content in water and manufacturing method thereof | |
| CN103175878B (en) | Reference half-cell and the electrochemical sensor with reference half-cell | |
| Miyahara et al. | Integrated enzyme FETs for simultaneous detections of urea and glucose | |
| CN107941876B (en) | Silver/silver chloride reference electrode and manufacturing method thereof | |
| CN108680628B (en) | Micro-nano sensor for detecting nutrient salt content in water and manufacturing method thereof | |
| CN107271525B (en) | Integrated ampere detection sensor for micro total analysis system chip | |
| CN104492509A (en) | Micro-fluidic chip having nano dendrite Raman substrate and manufacturing method thereof | |
| CN108362627B (en) | Resistance type micro sensor | |
| CN108120755A (en) | Detection device and its application | |
| CN210109021U (en) | Integrated micro-nano sensor | |
| US10612078B2 (en) | Integrated electrochemical nucleic acid based sensors and related platforms | |
| CN104122386A (en) | Sensor array chip | |
| CN108459061B (en) | Silver/silver chloride reference electrode and manufacturing method thereof | |
| Yin et al. | Batch microfabrication and testing of a novel silicon-base miniaturized reference electrode with an ion-exchanging nanochannel array for nitrite determination | |
| CN208672562U (en) | For detecting the micro-nano sensor of Organic substance in water content | |
| Ul Haque et al. | A MEMS fabricated cell electrophysiology biochip for in silico calcium measurements | |
| US20230114495A1 (en) | Microfluidic devices comprising electrochemical sensors | |
| US20110285409A1 (en) | Nanofluidic channel with embedded transverse nanoelectrodes and method of fabricating for same | |
| CN110207737B (en) | Microstrip antenna sensor system with linear array structure, sensor, detection method and preparation method | |
| Zhang et al. | Batch fabrication of miniaturized Ag/AgCl reference electrode with ion exchanging micro-nano-pores by silicon-base double-side anisotropic etching process | |
| CN113138049A (en) | Integrated micro-nano sensor for water body temperature and salt depth detection and manufacturing method thereof | |
| CN207163965U (en) | A kind of integrated form ampere detection sensor for micro-total analysis system chip |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: NINGBO JINCHENG ELECTRONIC TECHNOLOGY Co.,Ltd. Assignor: Ningbo University Contract record no.: X2023980035528 Denomination of utility model: An integrated micro/nano sensor Granted publication date: 20200221 License type: Common License Record date: 20230515 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| AV01 | Patent right actively abandoned |
Granted publication date: 20200221 Effective date of abandoning: 20231121 |
|
| AV01 | Patent right actively abandoned |
Granted publication date: 20200221 Effective date of abandoning: 20231121 |
|
| AV01 | Patent right actively abandoned | ||
| AV01 | Patent right actively abandoned |