CN112903727A - Transmission electron microscope electrochemical detection chip and manufacturing method thereof - Google Patents

Transmission electron microscope electrochemical detection chip and manufacturing method thereof Download PDF

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Publication number
CN112903727A
CN112903727A CN202110331063.5A CN202110331063A CN112903727A CN 112903727 A CN112903727 A CN 112903727A CN 202110331063 A CN202110331063 A CN 202110331063A CN 112903727 A CN112903727 A CN 112903727A
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silicon substrate
chip
window
electrode
electron microscope
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廖洪钢
邓俊先
江友红
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Xiamen University
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Xiamen University
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/02—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material
    • G01N23/04—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by transmitting the radiation through the material and forming images of the material
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20008—Constructional details of analysers, e.g. characterised by X-ray source, detector or optical system; Accessories therefor; Preparing specimens therefor
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
    • G01N23/20—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by using diffraction of the radiation by the materials, e.g. for investigating crystal structure; by using scattering of the radiation by the materials, e.g. for investigating non-crystalline materials; by using reflection of the radiation by the materials
    • G01N23/20058—Measuring diffraction of electrons, e.g. low energy electron diffraction [LEED] method or reflection high energy electron diffraction [RHEED] method
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/416—Systems

Abstract

The invention belongs to the technical field of electrochemical chips, and particularly relates to a transmission electron microscope electrochemical detection chip and a manufacturing method thereof. The transmission electron microscope electrochemical detection chip comprises an upper chip and a lower chip, wherein the upper chip and the lower chip are silicon substrates, the front surfaces of the upper chip and the lower chip are respectively provided with an insulating layer, the front surfaces of the upper chip and the lower chip are fixedly bonded through a bonding layer, and the upper chip, the lower chip and the bonding layer form a cavity together; the upper piece is provided with a sample injection port and a first window, the lower piece is provided with a working electrode, a reference electrode, a counter electrode, a second window and a thermometer, and the working electrode, the reference electrode and the counter electrode are all erected on the second window. The thermometer is arranged on the lower piece of the transmission electron microscope electrochemical detection chip, can be used for monitoring the reaction temperature in real time, and is convenient for a user to better know the heat absorption and release reaction type of the electrochemical reaction and the influence of the temperature on the electrochemical reaction. The manufacturing method provided by the invention can be used for manufacturing the transmission electron microscope electrochemical detection chip.

Description

Transmission electron microscope electrochemical detection chip and manufacturing method thereof
Technical Field
The invention belongs to the technical field of electrochemical chips, and particularly relates to a transmission electron microscope electrochemical detection chip and a manufacturing method thereof.
Background
In the development process of science and technology, electrochemistry plays an important role in the fields of electrolysis, electroplating, chemical power supply, electric analysis, metal corrosion and protection and the like. However, with the progress of science and technology, the application range of electrochemistry has been expanded to the fields of environmental protection, electronics, energy, materials, chemical engineering, metallurgy, chemical synthesis and the like. The redox process of metal atoms, organic molecules and other microscopic particles is observed from a microscopic angle through a transmission electron microscope electrochemical detection chip, and the information is necessary for technical principle analysis in the fields of materials, energy sources and the like.
The invention patent application CN110736760A discloses an electrochemical detection chip, which has several disadvantages, among which, the most important point is that the electrochemical detection chip does not have a temperature detection function, and it is inconvenient for users to know the type of the heat absorption and release reaction of the electrochemical reaction and the influence of the temperature on the electrochemical reaction.
Disclosure of Invention
In order to solve the above problems, the present invention provides a chip for electrochemical detection by a transmission electron microscope with temperature detection function, and also provides a method for manufacturing the chip for electrochemical detection by a transmission electron microscope, which can be used for manufacturing the chip for electrochemical detection by a transmission electron microscope.
Specifically, the technical scheme of the invention is as follows:
a chip for electrochemical detection of a transmission electron microscope comprises an upper chip and a lower chip, wherein the upper chip and the lower chip are silicon substrates, the front surfaces of the upper chip and the lower chip are respectively provided with an insulating layer, the front surfaces of the upper chip and the lower chip are fixedly bonded through a bonding layer, and the upper chip, the lower chip and the bonding layer jointly form a cavity; the upper piece is provided with a sample injection port and a first window, the lower piece is provided with a working electrode, a reference electrode, a counter electrode, a second window and a thermometer, and the working electrode, the reference electrode and the counter electrode are all erected on the second window.
Preferably, the working electrode is located at the center of the second window, the counter electrode and the working electrode are arranged on the second window side by side, the reference electrode is arranged on the second window in a manner of being perpendicular to the working electrode, and the thermometer is arranged on the second window and is opposite to the counter electrode and the working electrode.
Preferably, the device further comprises a carbon electrode, and the carbon electrode is covered on the working electrode.
Preferably, the thermometer is composed of a platinum metal film pattern.
A manufacturing method of a transmission electron microscope electrochemical detection chip comprises the following steps:
s1: processing a sample injection port and a first window on a silicon substrate A with insulating layers on the front and back surfaces to manufacture an upper wafer;
s2: processing a working electrode, a reference electrode, a counter electrode, a second window and a thermometer on a silicon substrate B with insulating layers on the front and back surfaces, and manufacturing a lower wafer;
s3: and fixedly bonding the upper sheet and the lower sheet through the bonding layer to obtain the transmission electron microscope electrochemical detection chip.
Preferably, step S2 includes:
s21: transferring the second window pattern from the photoetching mask plate to the back surface of a silicon substrate B with insulating layers on the front and back surfaces by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B1;
s22: removing the insulating layer corresponding to the second window on the back surface of the silicon substrate B1 by adopting a reactive ion etching process, and then removing the photoresist to obtain a silicon substrate B2;
s23: removing the substrate silicon corresponding to the second window from the silicon substrate B2 by adopting a wet etching process, and washing with deionized water to obtain a silicon substrate B3;
s24: transferring the patterns of the working electrode, the reference electrode and the counter electrode to the front surface of a silicon substrate B3 from a photoetching mask plate by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B4;
s25: sputtering a layer of electrode material film on the front surface of a silicon substrate B4 by adopting a direct current magnetron sputtering process, soaking the silicon substrate B4 in acetone, washing the silicon substrate B4 with deionized water, and removing photoresist to obtain a silicon substrate B5;
s26: transferring the thermometer pattern from the photoetching mask plate to the front surface of a silicon substrate B5 by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B6;
s27: adopting a direct-current magnetron sputtering process, sputtering a platinum metal film on the front surface of a silicon substrate B6, soaking the silicon substrate B6 in acetone, washing the silicon substrate B6 with deionized water, and removing photoresist to obtain a silicon substrate B7;
s28: the silicon substrate B7 was subjected to laser scribing to obtain a lower piece.
Preferably, step S2 includes:
s21: transferring the second window pattern from the photoetching mask plate to the back surface of a silicon substrate B with insulating layers on the front and back surfaces by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B1;
s22: removing the insulating layer corresponding to the second window on the back surface of the silicon substrate B1 by adopting a reactive ion etching process, and then removing the photoresist to obtain a silicon substrate B2;
s23: removing the substrate silicon corresponding to the second window from the silicon substrate B2 by adopting a wet etching process, and washing with deionized water to obtain a silicon substrate B3;
s24: transferring the patterns of the working electrode, the reference electrode and the counter electrode to the front surface of a silicon substrate B3 from a photoetching mask plate by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B4;
s25: sputtering a layer of electrode material film on the front surface of a silicon substrate B4 by adopting a direct current magnetron sputtering process, soaking the silicon substrate B4 in acetone, washing the silicon substrate B4 with deionized water, and removing photoresist to obtain a silicon substrate B5;
s31: sputtering a carbon film on the front surface of a silicon substrate B5 by adopting a radio frequency magnetron sputtering process;
s32: transferring the carbon electrode pattern from the photoetching mask plate to the front surface of a silicon substrate B5 by adopting a photoetching process, and removing the carbon film which is not protected by the photoresist by using a reactive ion etching machine to obtain a silicon substrate B6';
s33: removing the photoresist to obtain a silicon substrate B7';
s34: transferring the thermometer pattern from the photoetching mask plate to the front surface of a silicon substrate B7' by adopting a photoetching process, developing in a positive photoresist developing solution, and cleaning the surface by using deionized water to obtain a silicon substrate B8;
s35: adopting a direct-current magnetron sputtering process, sputtering a platinum metal film on the front surface of a silicon substrate B8, soaking the silicon substrate B8 in acetone, washing the silicon substrate B8 with deionized water, and removing photoresist to obtain a silicon substrate B9;
s36: the silicon substrate B9 was subjected to laser scribing to obtain a lower piece.
Preferably, the photolithography process used in step S21 is: and (3) exposing in a hard contact mode of an ultraviolet lithography machine, wherein the developing time is 60 seconds, and the exposing time is 15 seconds.
Preferably, the wet etching process adopted in step S23 is: and (3) etching by using a potassium hydroxide solution with the mass percentage concentration of 20%, wherein the etching temperature is 80 ℃, and the etching time is 2 hours.
Preferably, step S32 includes: and etching the carbon film which is not protected by the photoresist in argon and oxygen, wherein the etching power is 50 watts, and the etching time is 30 seconds.
The electrochemical detection chip for the transmission electron microscope provided by the invention adopts a three-electrode system of the reference electrode, the working electrode and the counter electrode, so that the electric field of the chip is stable, and the chip can be used for observing the oxidation-reduction reaction of microscopic particles under different potentials. Furthermore, the thermometer is arranged on the lower piece of the transmission electron microscope electrochemical detection chip, and can be used for monitoring the reaction temperature in real time, so that a user can better know the heat absorption and release reaction type of the electrochemical reaction and the influence of the temperature on the electrochemical reaction. The manufacturing method of the transmission electron microscope electrochemical detection chip provided by the invention can be used for manufacturing the transmission electron microscope electrochemical detection chip.
Drawings
FIG. 1 is a block diagram of a first embodiment of the present invention;
FIG. 2 is an enlarged view of portion A of FIG. 1;
FIG. 3 is a top view of a lower plate in accordance with an embodiment of the present invention;
FIG. 4 is an enlarged view of portion B of FIG. 3;
FIG. 5 is a schematic cross-sectional view of a silicon substrate according to an embodiment of the present invention;
FIG. 6 is a flow chart of a method of the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and the embodiments.
The first embodiment is as follows:
as shown in fig. 1 to 4, a chip for electrochemical detection by a transmission electron microscope includes an upper chip 1 and a lower chip 2, where the upper chip 1 and the lower chip 2 are silicon substrates with insulating layers on both front and back sides.
Those skilled in the art are familiar with: the general structure of the silicon substrate is shown in fig. 5, and includes a base silicon 31 in the middle, an insulating layer 32 on the front side, and an insulating layer 33 on the back side. In this embodiment, the insulating layer is a silicon nitride layer or a silicon oxide layer, which allows electron beams to penetrate while preventing the reaction solution inside the chip from volatilizing to damage the vacuum environment inside the electron microscope, thereby facilitating the imaging of the transmission electron microscope. In the present embodiment, the thickness of the insulating layer is 5 to 200 nm, and the thickness of the silicon substrate is 50 to 500 μm.
The front surface of the upper sheet 1 is bonded to the front surface of the lower sheet 2 by an adhesive layer (not shown), and the upper sheet 1, the lower sheet 2 and the adhesive layer together form an ultra-thin chamber. When the adhesive layer is provided, the adhesive layer is provided on the upper sheet 1 or the lower sheet 2, and then the upper sheet 1 and the lower sheet 2 are bonded, and since the structure of the lower sheet 2 is more complicated than that of the upper sheet 1, it is preferable to provide the adhesive layer on the upper sheet 1 first. In this embodiment, the size of the lower sheet is 2mm × 2mm to 10mm × 10mm, preferably 4mm × 8mm, and is limited by the area of the window of the mirror, if the chip is too large, the chip is wasted in the portion of the chip that is not in the observable area, and if the chip is too small, the distance between the electrodes is inevitably too small, which is not favorable for observation; the upper panel 1 is slightly smaller in size than the lower panel 2 in order to secure the upper panel 1 provided with an adhesive layer to the lower panel 2.
In this embodiment, a low-melting, viscous, and conductive material is used to form the adhesive layer by an evaporation process. The bonding layer is a metal bonding layer, the thickness of the bonding layer is 50-2000 nanometers, the bonding layer is made of low-melting-point metal, and indium, tin or aluminum is preferred.
The upper sheet 1 is provided with the sample injection ports 11 and the first window 12, in the embodiment, the number of the sample injection ports 11 is two, and the two sample injection ports 11 are symmetrically arranged relative to the first window 12, so that the structure is simple, and the manufacturing and the use are convenient.
The lower sheet 2 is provided with a working electrode 21, a reference electrode 22, a counter electrode 23, a second window 24 and a micro thermometer 25, and the working electrode 21, the reference electrode 22 and the counter electrode 23 are all arranged on the second window 24. In the present embodiment, the material of each electrode is gold, silver, copper or titanium, and the thickness is 30 to 200 nm.
The electrochemical detection chip for the transmission electron microscope provided by the invention adopts a three-electrode system of the reference electrode, the working electrode and the counter electrode, so that the electric field of the chip is stable, and the chip can be used for observing the oxidation-reduction reaction of microscopic particles under different potentials. Furthermore, the thermometer is arranged on the lower piece of the transmission electron microscope electrochemical detection chip, and can be used for monitoring the reaction temperature in real time, so that a user can better know the heat absorption and release reaction type of the electrochemical reaction and the influence of the temperature on the electrochemical reaction.
In this embodiment, the substrate silicon and the back insulating layer in the center of the upper sheet 1 are removed, and the front insulating layer in the center of the upper sheet 1 is left to form a first window 12; removing the substrate silicon and the back insulating layer in the center of the lower sheet 2, and remaining the front insulating layer in the center of the lower sheet 2 to form a second window 24; the ultrathin cavity formed by the upper sheet 1, the lower sheet 2 and the metal bonding layer is a uniform thin cavity.
Further, the first window 12 and the second window 24 are respectively arranged in the center of the upper sheet 1 and the lower sheet 2, and the center of the second window 24 is aligned with the center of the first window 12 up and down, so that the use is convenient. In other embodiments, the first window 12 and the second window 24 may be offset.
In the present embodiment, the first windows 12 and the second windows 24 are square, and the sizes of the first windows 12 and the second windows 24 are 5 micrometers by 5 micrometers to 100 micrometers by 100 micrometers, preferably 20 micrometers by 50 micrometers; the first window 12 and the second window 24 should not be too large in size, otherwise they are easily broken in the process flow of photolithography, etching, etc. In other embodiments, the first window 12 and the second window 24 may take other shapes and sizes. The tip of the working electrode 21 is preferably entirely on the second window 24 so as to observe the electrochemical reaction on the working electrode 21, and if the tip of the working electrode 21 is too small, the effective area to be observed is too small, and in this embodiment, the narrowest width of the tip of the working electrode 21 is 3 to 15 μm corresponding to the size of the second window 24.
Further, the working electrode 21 is positioned at the center of the second window 24 so as to observe the electrochemical reaction occurring on the working electrode 21. The counter electrode 23 and the working electrode 21 are arranged on the second window 24 side by side (namely, the counter electrode 23 and the working electrode 21 are arranged in parallel), and the distance between the counter electrode 23 and the working electrode 21 is 20-5000 micrometers. The reference electrode 22 is arranged on the second window 24 perpendicularly to the working electrode 21 (of course, the reference electrode 22 is also perpendicular to the counter electrode 23), the micro thermometer 25 is arranged on the second window 24 so as to measure the reaction temperature within the second window 24, and the micro thermometer 25 is arranged opposite (i.e., face-to-face) the counter electrode 23 and the working electrode 21 so as to fully utilize the space above the second window 24.
Further, the micro thermometer 25 is composed of a platinum metal film pattern, and the temperature change of the reaction micro-zone is determined by measuring the resistance change of the platinum metal film at different temperatures. The pure platinum film is easy to process, the resistance stability of the platinum wire in cold and hot circulation is high, and the resistance and the temperature have good linear relation. In other embodiments, the micro-thermometer 25 may be made of other materials that change resistance with temperature. In the present embodiment, the thickness of the platinum metal film is 30 to 500 nm; the thickness variance of the platinum film is large, the platinum metal film is not too thin, otherwise the temperature measurement accuracy is influenced; the platinum film has internal stress, and the platinum metal film is not suitable to be too thick, otherwise the platinum metal film is easy to break.
Further, the platinum metal film pattern is in a regular square wave shape. The platinum metal film in a regular shape can enable temperature measurement to be more uniform and accurate, and the thinner the platinum wire is, the larger the contact area between the platinum metal film and the outside is, and the more favorable the measurement of the environment temperature is. In other embodiments, other shapes of platinum metal films may be used.
Example two:
the difference between this embodiment and the first embodiment is: the chip for electrochemical detection by transmission electron microscope further comprises a carbon electrode (not shown), which is covered on the working electrode 21 and is not in contact with the counter electrode 23. The introduction of the carbon electrode can effectively improve the imaging resolution and reduce the background noise.
Further, the carbon electrode is composed of a carbon film plated on the working electrode 21, facilitating the manufacture. In this embodiment, the thickness of the carbon film is 10 to 80 nm.
Example three:
the invention also provides a manufacturing method of the transmission electron microscope electrochemical detection chip, and the manufacturing method can be used for manufacturing the transmission electron microscope electrochemical detection chip described in the first embodiment.
As shown in fig. 6, the manufacturing method includes the steps of:
s1: and processing a sample injection port and a first window on a silicon substrate A with insulating layers on the front and back surfaces to manufacture an upper wafer.
S2: and processing a working electrode, a reference electrode, a counter electrode, a second window and a thermometer on a silicon substrate B with insulating layers on the front and back surfaces, and manufacturing a lower wafer.
S3: and bonding the upper sheet and the lower sheet through the bonding layer to obtain the transmission electron microscope electrochemical detection chip. The upper sheet, the lower sheet and the adhesive layer together form an ultra-thin chamber.
Further, step S1 includes:
s11: and transferring the first window pattern and the sample injection port pattern from the photoetching mask plate to the silicon substrate A with the insulating layer on the front surface and the back surface by adopting a photoetching process, and developing in a positive photoresist developing solution to obtain the silicon substrate A1. Preferably, the photolithography process is exposure in a hard contact mode of an ultraviolet lithography machine, the development time is 50 seconds, and the exposure time is 15 seconds.
S12: and removing the insulating layer corresponding to the first window and the sample injection port on the back surface of the silicon substrate A1 by adopting a reactive ion etching process, soaking the silicon substrate A1 in acetone, washing the silicon substrate A1 with deionized water, and removing the photoresist to obtain the silicon substrate A2.
S13: and (3) removing the substrate silicon corresponding to the first window and the sample injection port from the silicon substrate A2 by adopting a wet etching process, and washing with deionized water to obtain the silicon substrate A3. Preferably, the etching is carried out by using a potassium hydroxide solution with the mass percentage concentration of 20%, the etching temperature is 80 ℃, and the etching time is 2 hours.
S14: and transferring the metal bonding layer pattern from the photoetching mask plate to the front surface of the silicon substrate A3 by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain the silicon substrate A4. Preferably, the photolithography process is exposure in a hard contact mode of an ultraviolet lithography machine, the development time is 50 seconds, and the exposure time is 15 seconds.
S15: and (3) evaporating a metal bonding material on the silicon substrate A4 to form a metal bonding layer by adopting a thermal evaporation coating process to obtain the silicon substrate A5.
S16: and laser scribing the silicon substrate A5 to obtain a top piece.
Step S2 includes:
s21: and transferring the second window pattern from the photoetching mask plate to the back surface of the silicon substrate B with the insulating layer on the front surface and the back surface by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain the silicon substrate B1. Preferably, the photolithography process is exposure in hard contact mode of a uv lithography machine, the photoresist used in the photolithography process is AZ5214E, the development time is 60 seconds, and the exposure time is 15 seconds.
S22: and removing the insulating layer corresponding to the second window on the back surface of the silicon substrate B1 by adopting a reactive ion etching process, and then removing the photoresist to obtain a silicon substrate B2.
S23: and (3) removing the substrate silicon corresponding to the second window from the silicon substrate B2 by adopting a wet etching process, and washing with deionized water to obtain a silicon substrate B3. Preferably, the etching is carried out by using a potassium hydroxide solution with the mass percentage concentration of 20%, the etching temperature is 80 ℃, and the etching time is 2 hours.
S24: and transferring the patterns of the working electrode, the reference electrode and the counter electrode to the front surface of the silicon substrate B3 from a photoetching mask plate by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain the silicon substrate B4.
S25: and (3) sputtering a layer of electrode material film on the front surface of the silicon substrate B4 by adopting a direct current magnetron sputtering process, soaking the silicon substrate B4 in acetone, washing the silicon substrate B4 with deionized water, and removing the photoresist to obtain the silicon substrate B5.
S26: and transferring the pattern of the minitype thermometer from the photoetching mask plate to the front surface of the silicon substrate B5 by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain the silicon substrate B6.
S27: and (3) sputtering a platinum metal film on the front surface of the silicon substrate B6 by adopting a direct current magnetron sputtering process, soaking the film in acetone, washing the film with deionized water, and removing the photoresist to obtain the silicon substrate B7.
S28: the silicon substrate B7 was subjected to laser scribing to obtain a lower piece.
Example four:
the invention also provides a manufacturing method of the transmission electron microscope electrochemical detection chip, and the manufacturing method can be used for manufacturing the transmission electron microscope electrochemical detection chip described in the second embodiment. The difference between the present embodiment and the third embodiment is:
step S2 includes:
s21: and transferring the second window pattern from the photoetching mask plate to the back surface of the silicon substrate B with the insulating layer on the front surface and the back surface by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain the silicon substrate B1. Preferably, the photolithography process is exposure in hard contact mode of a uv lithography machine, the photoresist used in the photolithography process is AZ5214E, the development time is 60 seconds, and the exposure time is 15 seconds.
S22: and removing the insulating layer corresponding to the second window on the back surface of the silicon substrate B1 by adopting a reactive ion etching process, and then removing the photoresist to obtain a silicon substrate B2.
S23: and (3) removing the substrate silicon corresponding to the second window from the silicon substrate B2 by adopting a wet etching process, and washing with deionized water to obtain a silicon substrate B3. Preferably, the etching is carried out by using a potassium hydroxide solution with the mass percentage concentration of 20%, the etching temperature is 80 ℃, and the etching time is 2 hours.
S24: and transferring the patterns of the working electrode, the reference electrode and the counter electrode to the front surface of the silicon substrate B3 from a photoetching mask plate by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain the silicon substrate B4.
S25: and (3) sputtering a layer of electrode material film on the front surface of the silicon substrate B4 by adopting a direct current magnetron sputtering process, soaking the silicon substrate B4 in acetone, washing the silicon substrate B4 with deionized water, and removing the photoresist to obtain the silicon substrate B5.
S31: and sputtering a carbon film on the front surface of the silicon substrate B5 by adopting a radio frequency magnetron sputtering process.
S32: and (3) transferring the carbon electrode pattern from the photoetching mask plate to the front side of the silicon substrate B5 by adopting a photoetching process, and then removing the carbon film which is not protected by the photoresist by using a reactive ion etching machine to obtain the silicon substrate B6', preferably, etching the carbon film which is not protected by the photoresist in argon and oxygen, wherein the etching power is 50 watts, and the etching time is 30 seconds.
S33: the photoresist was removed to obtain a silicon substrate B7'.
S34: and transferring the micro thermometer pattern from the photoetching mask plate to the front surface of the silicon substrate B7' by adopting a photoetching process, developing in a positive photoresist developing solution, and cleaning the surface by using deionized water to obtain the silicon substrate B8.
S35: and (3) sputtering a platinum metal film on the front surface of the silicon substrate B8 by adopting a direct current magnetron sputtering process, soaking the film in acetone, washing the film with deionized water, and removing the photoresist to obtain the silicon substrate B9.
S36: the silicon substrate B9 was subjected to laser scribing to obtain a lower piece.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be understood that any modification, equivalent replacement, improvement, etc. made by those skilled in the art after reading the specification, which are within the spirit and principle of the present invention, should be included in the protection scope of the present invention.

Claims (10)

1. A chip for electrochemical detection of a transmission electron microscope comprises an upper chip and a lower chip, wherein the upper chip and the lower chip are silicon substrates, the front surfaces of the upper chip and the lower chip are respectively provided with an insulating layer, the front surfaces of the upper chip and the lower chip are fixedly bonded through a bonding layer, and the upper chip, the lower chip and the bonding layer jointly form a cavity; the upper piece is provided with a sample injection port and a first window, and the lower piece is provided with a working electrode, a reference electrode, a counter electrode, a second window and a thermometer, and the working electrode, the reference electrode and the counter electrode are all erected on the second window.
2. The chip for electrochemical detection by means of transmission electron microscope as claimed in claim 1, wherein the working electrode is located in the center of the second window, the counter electrode and the working electrode are arranged side by side on the second window, the reference electrode is arranged on the second window perpendicular to the working electrode, and the thermometer is arranged on the second window and is opposite to the counter electrode and the working electrode.
3. The TEM electrochemical detection chip as claimed in claim 1, further comprising a carbon electrode, wherein the carbon electrode covers the working electrode.
4. The TEM electrochemical detection chip as claimed in claim 1, wherein the thermometer is formed by a platinum metal film pattern.
5. A manufacturing method of a transmission electron microscope electrochemical detection chip is characterized by comprising the following steps:
s1: processing a sample injection port and a first window on a silicon substrate A with insulating layers on the front and back surfaces to manufacture an upper wafer;
s2: processing a working electrode, a reference electrode, a counter electrode, a second window and a thermometer on a silicon substrate B with insulating layers on the front and back surfaces, and manufacturing a lower wafer;
s3: and fixedly bonding the upper sheet and the lower sheet through the bonding layer to obtain the transmission electron microscope electrochemical detection chip.
6. The method for manufacturing the transmission electron microscope electrochemical detection chip according to claim 5, wherein the step S2 includes:
s21: transferring the second window pattern from the photoetching mask plate to the back surface of a silicon substrate B with insulating layers on the front and back surfaces by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B1;
s22: removing the insulating layer corresponding to the second window on the back surface of the silicon substrate B1 by adopting a reactive ion etching process, and then removing the photoresist to obtain a silicon substrate B2;
s23: removing the substrate silicon corresponding to the second window from the silicon substrate B2 by adopting a wet etching process, and washing with deionized water to obtain a silicon substrate B3;
s24: transferring the patterns of the working electrode, the reference electrode and the counter electrode to the front surface of a silicon substrate B3 from a photoetching mask plate by adopting a photoetching process, developing in positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B4;
s25: sputtering a layer of electrode material film on the front surface of a silicon substrate B4 by adopting a direct current magnetron sputtering process, soaking the silicon substrate B4 in acetone, washing the silicon substrate B4 with deionized water, and removing photoresist to obtain a silicon substrate B5;
s26: transferring the thermometer pattern from the photoetching mask plate to the front surface of a silicon substrate B5 by adopting a photoetching process, developing in a positive photoresist developing solution, and washing with deionized water to obtain a silicon substrate B6;
s27: adopting a direct-current magnetron sputtering process, sputtering a platinum metal film on the front surface of a silicon substrate B6, soaking the silicon substrate B6 in acetone, washing the silicon substrate B6 with deionized water, and removing photoresist to obtain a silicon substrate B7;
s28: the silicon substrate B7 was subjected to laser scribing to obtain a lower piece.
7. The method for manufacturing the transmission electron microscope electrochemical detection chip as claimed in claim 6, wherein steps S26 to S28 are replaced with:
s31: sputtering a carbon film on the front surface of a silicon substrate B5 by adopting a radio frequency magnetron sputtering process;
s32: transferring the carbon electrode pattern from the photoetching mask plate to the front surface of a silicon substrate B5 by adopting a photoetching process, and removing the carbon film which is not protected by the photoresist by using a reactive ion etching machine to obtain a silicon substrate B6';
s33: removing the photoresist to obtain a silicon substrate B7';
s34: transferring the thermometer pattern from the photoetching mask plate to the front surface of a silicon substrate B7' by adopting a photoetching process, developing in a positive photoresist developing solution, and cleaning the surface by using deionized water to obtain a silicon substrate B8;
s35: adopting a direct-current magnetron sputtering process, sputtering a platinum metal film on the front surface of a silicon substrate B8, soaking the silicon substrate B8 in acetone, washing the silicon substrate B8 with deionized water, and removing photoresist to obtain a silicon substrate B9;
s36: the silicon substrate B9 was subjected to laser scribing to obtain a lower piece.
8. The method for manufacturing the chip for electrochemical detection by transmission electron microscope according to claim 6, wherein the photolithography process used in step S21 is: and (3) exposing in a hard contact mode of an ultraviolet lithography machine, wherein the developing time is 60 seconds, and the exposing time is 15 seconds.
9. The method for manufacturing the chip for electrochemical detection by transmission electron microscope according to claim 6, wherein the wet etching process adopted in step S23 is: and (3) etching by using a potassium hydroxide solution with the mass percentage concentration of 20%, wherein the etching temperature is 80 ℃, and the etching time is 2 hours.
10. The method for manufacturing the transmission electron microscope electrochemical detection chip according to claim 7, wherein the step S32 includes: and etching the carbon film which is not protected by the photoresist in argon and oxygen, wherein the etching power is 50 watts, and the etching time is 30 seconds.
CN202110331063.5A 2021-03-29 2021-03-29 Transmission electron microscope electrochemical detection chip and manufacturing method thereof Pending CN112903727A (en)

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