Transmission electron microscope electrochemical detection chip and manufacturing method thereof

Abstract

The present invention belongs to the technical field of electrochemical chips, and specifically relates to a transmission electron microscope electrochemical detection chip and a manufacturing method thereof. The transmission electron microscope electrochemical detection chip comprises an upper sheet and a lower sheet, both of which are silicon substrates with insulating layers on both the front and back sides, the front side of the upper sheet and the front side of the lower sheet are fixedly bonded by an adhesive layer, and the upper sheet, the lower sheet and the adhesive layer together constitute a chamber; the upper sheet is provided with a sample injection port and a first window, and the lower sheet 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 set on the second window. The lower sheet of the transmission electron microscope electrochemical detection chip provided by the present invention is provided with a thermometer, which can be used to monitor the reaction temperature in real time, so that the user can better understand the endothermic and exothermic reaction types of electrochemical reactions and the influence of temperature on electrochemical reactions. The manufacturing method provided by the present invention can be used to manufacture the aforementioned transmission electron microscope electrochemical detection chip.

Description

Technical Field

[0001] The invention belongs to the technical field of electrochemical chips, and in particular relates to a transmission electron microscope electrochemical detection chip and a manufacturing method thereof. Background Art

[0002] In the process of scientific and technological development, electrochemistry has played an important role in the fields of electrolysis, electroplating, chemical power supply, electroanalysis, metal corrosion and protection. However, with the progress of science and technology, the application scope of electrochemistry has expanded to environmental protection, electronics, energy, materials, chemical industry, metallurgy and chemical synthesis. Through the transmission electron microscope electrochemical detection chip, the redox process of metal atoms, organic molecules and other microscopic particles can be observed from a microscopic perspective. This information is very necessary for the analysis of technical principles in the fields of materials, energy, etc.

[0003] Invention patent application CN110736760A discloses an electrochemical detection chip, which has several shortcomings. The most important one is that the electrochemical detection chip does not have a temperature detection function, which makes it difficult for users to understand the type of endothermic and exothermic reactions of electrochemical reactions and the influence of temperature on electrochemical reactions. Summary of the invention

[0004] To solve the above problems, the present invention provides a transmission electron microscope electrochemical detection chip with temperature detection function, and also provides a method for manufacturing the transmission electron microscope electrochemical detection chip, which can be used to manufacture the aforementioned transmission electron microscope electrochemical detection chip.

[0005] Specifically, the technical solution of the present invention is:

[0006] A transmission electron microscope electrochemical detection chip comprises an upper chip and a lower chip, both of which are silicon substrates with insulating layers on both the front and back sides, the front side of the upper chip is fixedly bonded to the front side of the lower chip by an adhesive layer, and the upper chip, the lower chip and the adhesive layer together form a chamber; the upper chip is provided with a sample injection port and a first window, the lower chip 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 mounted on the second window.

[0007] Preferably, the working electrode is located in the center of the second viewing window, the counter electrode and the working electrode are arranged side by side on the second viewing window, the reference electrode is arranged on the second viewing window perpendicular to the working electrode, and the thermometer is arranged on the second viewing window and opposite to the counter electrode and the working electrode.

[0008] Preferably, a carbon electrode is further included, and the carbon electrode covers the working electrode.

[0009] Preferably, the thermometer is formed of a platinum metal film pattern.

[0010] A method for manufacturing a transmission electron microscope electrochemical detection chip, comprising:

[0011] S1: Processing a sample injection port and a first window on a silicon substrate A provided with insulating layers on both the front and back sides to manufacture an upper wafer;

[0012] S2: A working electrode, a reference electrode, a counter electrode, a second window and a thermometer are processed on a silicon substrate B provided with insulating layers on both the front and back sides to manufacture a lower wafer;

[0013] S3: The upper sheet and the lower sheet are fixedly bonded by an adhesive layer to obtain a transmission electron microscope electrochemical detection chip.

[0014] Preferably, step S2 comprises:

[0015] S21: using a photolithography process, transferring the second window pattern from the photolithography mask to the back side of the silicon substrate B having an insulating layer on both the front and back sides, developing in a positive photoresist developer, and rinsing with deionized water to obtain a silicon substrate B1;

[0016] S22: using a reactive ion etching process to remove the insulating layer on the back side of the silicon substrate B1 corresponding to the second window, and then removing the photoresist to obtain a silicon substrate B2;

[0017] S23: using a wet etching process to remove the base silicon of the silicon substrate B2 and the second window, and then washing with deionized water to obtain a silicon substrate B3;

[0018] S24: using a photolithography process, transferring the working electrode, reference electrode and counter electrode patterns from the photolithography mask to the front side of the silicon substrate B3, developing in a positive photoresist developer, and rinsing with deionized water to obtain a silicon substrate B4;

[0019] S25: using a DC magnetron sputtering process, a layer of electrode material film is sputtered on the front side of the silicon substrate B4, and then soaked in acetone, rinsed with deionized water, and the photoresist is removed to obtain a silicon substrate B5;

[0020] S26: using a photolithography process, transferring the thermometer pattern from the photolithography mask to the front side of the silicon substrate B5, developing it in a positive photoresist developer, and rinsing it with deionized water to obtain a silicon substrate B6;

[0021] S27: Using a DC magnetron sputtering process, a layer of platinum metal film is sputtered on the front of the silicon substrate B6, and then the silicon substrate B6 is soaked in acetone and rinsed with deionized water to remove the photoresist, thereby obtaining a silicon substrate B7;

[0022] S28: Laser scribing the silicon substrate B7 to obtain a lower wafer.

[0023] Preferably, step S2 comprises:

[0024] S21: using a photolithography process, transferring the second window pattern from the photolithography mask to the back side of the silicon substrate B having an insulating layer on both the front and back sides, developing in a positive photoresist developer, and rinsing with deionized water to obtain a silicon substrate B1;

[0025] S22: using a reactive ion etching process to remove the insulating layer on the back side of the silicon substrate B1 corresponding to the second window, and then removing the photoresist to obtain a silicon substrate B2;

[0026] S23: using a wet etching process to remove the base silicon of the silicon substrate B2 and the second window, and then washing with deionized water to obtain a silicon substrate B3;

[0027] S24: using a photolithography process, transferring the working electrode, reference electrode and counter electrode patterns from the photolithography mask to the front side of the silicon substrate B3, developing in a positive photoresist developer, and rinsing with deionized water to obtain a silicon substrate B4;

[0028] S25: using a DC magnetron sputtering process, a layer of electrode material film is sputtered on the front side of the silicon substrate B4, and then soaked in acetone, rinsed with deionized water, and the photoresist is removed to obtain a silicon substrate B5;

[0029] S31: Using radio frequency magnetron sputtering technology, a carbon film is sputtered on the front side of the silicon substrate B5;

[0030] S32: using a photolithography process to transfer the carbon electrode pattern from the photolithography mask to the front side of the silicon substrate B5, and then using a reactive ion etcher to remove the carbon film not protected by the photoresist to obtain a silicon substrate B6';

[0031] S33: removing the photoresist to obtain a silicon substrate B7';

[0032] S34: using a photolithography process, transferring the thermometer pattern from the photolithography mask to the front side of the silicon substrate B7', developing it in a positive photoresist developer, and cleaning the surface with deionized water to obtain a silicon substrate B8;

[0033] S35: using a DC magnetron sputtering process, sputtering a layer of platinum metal film on the front side of the silicon substrate B8, soaking it in acetone, rinsing it with deionized water, removing the photoresist, and obtaining a silicon substrate B9;

[0034] S36: Laser scribing the silicon substrate B9 to obtain a lower wafer.

[0035] Preferably, the photolithography process used in step S21 is: exposure in the hard contact mode of the ultraviolet photolithography machine, the development time is 60 seconds, and the exposure time is 15 seconds.

[0036] Preferably, the wet etching process adopted in step S23 is: etching with a potassium hydroxide solution having a mass percentage concentration of 20%, the etching temperature is 80° C., and the etching time is 2 hours.

[0037] Preferably, step S32 comprises: etching the carbon film not protected by the photoresist in argon and oxygen, with an etching power of 50 watts and an etching time of 30 seconds.

[0038] The transmission electron microscope electrochemical detection chip provided by the present invention adopts a three-electrode system of a reference electrode, a working electrode and a counter electrode, so that the chip electric field is stable and can be used to observe the redox reactions of microscopic particles at different potentials. Furthermore, the lower plate of the transmission electron microscope electrochemical detection chip provided by the present invention is provided with a thermometer, which can be used to monitor the reaction temperature in real time, so that the user can better understand the type of endothermic and exothermic reaction of the electrochemical reaction and the influence of temperature on the electrochemical reaction. The manufacturing method of the transmission electron microscope electrochemical detection chip provided by the present invention can be used to manufacture the aforementioned transmission electron microscope electrochemical detection chip. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] Figure 1 This is a structural diagram of Embodiment 1 of the present invention;

[0040] Figure 2 for Figure 1 A magnified view of part A;

[0041] Figure 3 This is a top view of a lower sheet according to an embodiment of the present invention;

[0042] Figure 4 for Figure 3 A magnified view of part B;

[0043] Figure 5 is a schematic cross-sectional view of a silicon substrate according to a first embodiment of the present invention;

[0044] Figure 6 The figure is a flow chart of the method of the present invention. DETAILED DESCRIPTION

[0045] The present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.

[0046] Embodiment 1:

[0047] like Figures 1 to 4 As shown, a transmission electron microscope electrochemical detection chip includes an upper chip 1 and a lower chip 2. The upper chip 1 and the lower chip 2 are both silicon substrates with insulating layers on the front and back sides.

[0048] It is well known to those skilled in the art that the general structure of the above silicon substrate is as follows: Figure 5As shown, it 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 prevents the reaction solution inside the chip from volatilizing and destroying the vacuum environment inside the electron microscope, while allowing the electron beam to pass through, facilitating transmission electron microscope imaging. In this embodiment, the thickness of the insulating layer is 5 to 200 nanometers, and the thickness of the silicon substrate is 50 to 500 microns.

[0049] The front of the upper sheet 1 is bonded to the front of the lower sheet 2 through an adhesive layer (not shown), and the upper sheet 1, the lower sheet 2 and the adhesive layer together constitute an ultra-thin chamber. When setting the adhesive layer, the adhesive layer is first set on the upper sheet 1 or the lower sheet 2, and then the upper sheet 1 and the lower sheet 2 are bonded. Since the structure of the lower sheet 2 is more complicated than that of the upper sheet 1, it is best to set the adhesive layer on the upper sheet 1 first. In this embodiment, the size of the lower sheet is 2mm*2mm~10mm*10mm, preferably 4mm*8mm. Limited by the area of ​​the electron microscope window, if the chip is too large, the part of the chip that is not in the observable area will be wasted. If the chip is too small, it will inevitably lead to too small spacing between the electrodes, which is not conducive to observation; the size of the upper sheet 1 is slightly smaller than the lower sheet 2, so that the upper sheet 1 with the adhesive layer can be fixed to the lower sheet 2.

[0050] In this embodiment, a low melting point, sticky and conductive material is used to form the bonding layer through a vapor deposition process. The bonding layer is a metal bonding layer with a thickness of 50 to 2000 nanometers, and the material is a low melting point metal, preferably indium, tin or aluminum.

[0051] The upper plate 1 is provided with a sample injection port 11 and a first viewing window 12. In this embodiment, there are two sample injection ports 11, which are symmetrically arranged about the first viewing window 12, and have a simple structure, and are easy to manufacture and use.

[0052] 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. The working electrode 21, the reference electrode 22 and the counter electrode 23 are all arranged on the second window 24. In this embodiment, the material of each electrode is a metal such as gold, silver, copper or titanium, and the thickness is 30 to 200 nanometers.

[0053] The transmission electron microscope electrochemical detection chip provided by the present invention adopts a three-electrode system of a reference electrode, a working electrode and a counter electrode, so that the chip electric field is stable and can be used to observe the redox reaction of microscopic particles at different potentials. Furthermore, the lower chip of the transmission electron microscope electrochemical detection chip provided by the present invention is provided with a thermometer, which can be used to monitor the reaction temperature in real time, so that users can better understand the type of endothermic and exothermic reaction of the electrochemical reaction and the influence of temperature on the electrochemical reaction.

[0054] In this embodiment, the base silicon and the reverse 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 remains, forming a first window 12; the base silicon and the reverse insulating layer in the center of the lower sheet 2 are removed, and the front insulating layer in the center of the lower sheet 2 remains, forming a second window 24; the ultra-thin chamber formed by the upper sheet 1, the lower sheet 2 and the metal bonding layer is a uniform thin cavity.

[0055] Furthermore, the first window 12 and the second window 24 are respectively arranged at 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 for ease of use. In other embodiments, the first window 12 and the second window 24 may also be offset.

[0056] In this embodiment, the first window 12 and the second window 24 are square, and the size of the first window 12 and the second window 24 is 5 microns * 5 microns to 100 microns * 100 microns, preferably 20 microns * 50 microns; the size of the first window 12 and the second window 24 should not be too large, otherwise it is easy to break during the process of photolithography, corrosion, etc. In other embodiments, the first window 12 and the second window 24 can also adopt other shapes and sizes. The tip of the working electrode 21 is preferably all on the second window 24, so as to observe the electrochemical reaction on the working electrode 21. If the tip of the working electrode 21 is too small, the observable effective area will be too small. In this embodiment, corresponding to the size of the second window 24, the narrowest width of the tip of the working electrode 21 is 3 to 15 microns.

[0057] Further, the working electrode 21 is located in the center of the second viewing 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 side by side on the second viewing window 24 (i.e., the counter electrode 23 and the working electrode 21 are arranged in parallel), and the counter electrode 23 is 20 to 5000 microns away from the working electrode 21. The reference electrode 22 is arranged perpendicularly to the working electrode 21 (of course, the reference electrode 22 is also perpendicular to the counter electrode 23) on the second viewing window 24, and the micro-thermometer 25 is arranged on the second viewing window 24 so as to measure the reaction temperature within the range of the second viewing window 24, and the micro-thermometer 25 is arranged opposite to the counter electrode 23 and the working electrode 21 (i.e., face to face) so as to make full use of the space above the second viewing window 24.

[0058] Furthermore, the micro-thermometer 25 is composed of a platinum metal film pattern, and the temperature change of the reaction micro-area is determined by measuring the resistance change of the platinum metal film at different temperatures. Pure platinum film is easy to process, and the resistance stability of platinum wire in hot and cold cycles is very high, and there is a good linear relationship between resistance and temperature. In other embodiments, the micro-thermometer 25 can also be made of other materials whose resistance changes with temperature. In this embodiment, the thickness of the platinum metal film is 30 to 500 nanometers; the thickness variance of the platinum film is large, and the platinum metal film should not be too thin, otherwise it will affect the accuracy of temperature measurement; the platinum film has internal stress, and the platinum metal film should not be too thick, otherwise it will easily break.

[0059] Furthermore, the platinum metal film pattern is a regular square wave shape. Using a platinum metal film with a regular shape can make the temperature measurement more uniform and accurate, and the thinner the platinum wire, the larger the contact area between the platinum metal film and the outside world, which is more conducive to measuring the ambient temperature. In other embodiments, platinum metal films of other shapes can also be used.

[0060] Embodiment 2:

[0061] The difference between this embodiment and the first embodiment is that the transmission electron microscope electrochemical detection chip further includes a carbon electrode (not shown), which covers the working electrode 21 and does not contact the counter electrode 23. The introduction of the carbon electrode can effectively improve the imaging resolution and reduce the background noise.

[0062] Furthermore, the carbon electrode is formed by a carbon film plated on the working electrode 21, which is easy to manufacture. In this embodiment, the thickness of the carbon film is 10 to 80 nanometers.

[0063] Embodiment three:

[0064] The present invention also provides a method for manufacturing a transmission electron microscope electrochemical detection chip, which can be used to manufacture the transmission electron microscope electrochemical detection chip described in the first embodiment.

[0065] like Figure 6 As shown, the manufacturing method comprises the following steps:

[0066] S1: A sample injection port and a first window are processed on a silicon substrate A with insulating layers on both the front and back sides to manufacture an upper wafer.

[0067] S2: A working electrode, a reference electrode, a counter electrode, a second window and a thermometer are processed on a silicon substrate B with insulating layers on both the front and back sides to manufacture a lower wafer.

[0068] S3: Bonding the upper sheet and the lower sheet through the bonding layer to obtain a transmission electron microscope electrochemical detection chip. The upper sheet, the lower sheet and the bonding layer together form an ultra-thin chamber.

[0069] Further, step S1 includes:

[0070] S11: Using a photolithography process, the first window pattern and the injection port pattern are transferred from the photolithography mask to the silicon substrate A with an insulating layer on both the front and back sides, and then developed in a positive photoresist developer to obtain a silicon substrate A1. Preferably, the photolithography process is to expose in the hard contact mode of an ultraviolet photolithography machine, with a development time of 50 seconds and an exposure time of 15 seconds.

[0071] S12: Reactive ion etching is used to remove the insulating layer on the back of the silicon substrate A1 corresponding to the first window and the injection port, and then the silicon substrate A1 is soaked in acetone and rinsed with deionized water to remove the photoresist to obtain the silicon substrate A2.

[0072] S13: Wet etching is performed on the silicon substrate A2 to remove the base silicon corresponding to the first window and the injection port, and then rinsed with deionized water to obtain the silicon substrate A3. Preferably, etching is performed with a potassium hydroxide solution having a mass percentage concentration of 20%, the etching temperature is 80° C., and the etching time is 2 hours.

[0073] S14: After transferring the metal bonding layer pattern from the photolithography mask to the front side of the silicon substrate A3 by photolithography, the pattern is developed in a positive photoresist developer and rinsed with deionized water to obtain the silicon substrate A4. Preferably, the photolithography process is exposure in the hard contact mode of the ultraviolet lithography machine, the development time is 50 seconds, and the exposure time is 15 seconds.

[0074] S15: using a thermal evaporation coating process to evaporate a metal bonding material on the silicon substrate A4 to form a metal bonding layer, thereby obtaining a silicon substrate A5.

[0075] S16: Laser scribing the silicon substrate A5 to obtain an upper wafer.

[0076] Step S2 includes:

[0077] S21: Using a photolithography process, the second window pattern is transferred from the photolithography mask to the back side of the silicon substrate B with an insulating layer on both the front and back sides, developed in a positive photoresist developer, and rinsed with deionized water to obtain a silicon substrate B1. Preferably, the photolithography process is exposure in the hard contact mode of an ultraviolet photolithography machine, the photoresist used in the photolithography process is AZ5214E, the development time is 60 seconds, and the exposure time is 15 seconds.

[0078] S22: using a reactive ion etching process to remove the insulating layer on the back side of the silicon substrate B1 corresponding to the second window, and then removing the photoresist to obtain a silicon substrate B2.

[0079] S23: using a wet etching process to remove the base silicon of the silicon substrate B2 and the second window, and then washing with deionized water to obtain a silicon substrate B3. Preferably, etching is performed with a potassium hydroxide solution having a mass percentage concentration of 20%, the etching temperature is 80°C, and the etching time is 2 hours.

[0080] S24: Using a photolithography process, the working electrode, reference electrode and counter electrode patterns are transferred from the photolithography mask to the front side of the silicon substrate B3, developed in a positive photoresist developer, and rinsed with deionized water to obtain a silicon substrate B4.

[0081] S25: A DC magnetron sputtering process is used to sputter a layer of electrode material film on the front side of the silicon substrate B4, and then the silicon substrate B4 is soaked in acetone and rinsed with deionized water to remove the photoresist to obtain a silicon substrate B5.

[0082] S26: Using a photolithography process, the micro-thermometer pattern is transferred from the photolithography mask to the front side of the silicon substrate B5, developed in a positive photoresist developer, and rinsed with deionized water to obtain a silicon substrate B6.

[0083] S27: Using a DC magnetron sputtering process, a layer of platinum metal film is sputtered on the front of the silicon substrate B6, then soaked in acetone, rinsed with deionized water, and the photoresist is removed to obtain a silicon substrate B7.

[0084] S28: Laser scribing the silicon substrate B7 to obtain a lower wafer.

[0085] Embodiment 4:

[0086] The present invention also provides a method for manufacturing a transmission electron microscope electrochemical detection chip, which can be used to manufacture the transmission electron microscope electrochemical detection chip described in Example 2. The difference between this embodiment and Example 3 is:

[0087] Step S2 includes:

[0088] S21: Using a photolithography process, the second window pattern is transferred from the photolithography mask to the back side of the silicon substrate B with an insulating layer on both the front and back sides, developed in a positive photoresist developer, and rinsed with deionized water to obtain a silicon substrate B1. Preferably, the photolithography process is exposure in the hard contact mode of an ultraviolet photolithography machine, the photoresist used in the photolithography process is AZ5214E, the development time is 60 seconds, and the exposure time is 15 seconds.

[0089] S22: using a reactive ion etching process to remove the insulating layer on the back side of the silicon substrate B1 corresponding to the second window, and then removing the photoresist to obtain a silicon substrate B2.

[0090] S23: using a wet etching process to remove the base silicon of the silicon substrate B2 and the second window, and then washing with deionized water to obtain a silicon substrate B3. Preferably, etching is performed with a potassium hydroxide solution having a mass percentage concentration of 20%, the etching temperature is 80°C, and the etching time is 2 hours.

[0091] S24: Using a photolithography process, the working electrode, reference electrode and counter electrode patterns are transferred from the photolithography mask to the front side of the silicon substrate B3, developed in a positive photoresist developer, and rinsed with deionized water to obtain a silicon substrate B4.

[0092] S25: A DC magnetron sputtering process is used to sputter a layer of electrode material film on the front side of the silicon substrate B4, and then the silicon substrate B4 is soaked in acetone and rinsed with deionized water to remove the photoresist to obtain a silicon substrate B5.

[0093] S31: A layer of carbon film is sputtered on the front side of the silicon substrate B5 using a radio frequency magnetron sputtering process.

[0094] S32: After transferring the carbon electrode pattern from the photolithography mask to the front side of the silicon substrate B5 by using a photolithography process, a reactive ion etcher is used to remove the carbon film not protected by the photoresist to obtain a silicon substrate B6'. Preferably, the carbon film not protected by the photoresist is etched in argon and oxygen with an etching power of 50 watts and an etching time of 30 seconds.

[0095] S33: removing the photoresist to obtain a silicon substrate B7'.

[0096] S34: Using a photolithography process, the micro thermometer pattern is transferred from the photolithography mask to the front side of the silicon substrate B7', developed in a positive photoresist developer, and the surface is cleaned with deionized water to obtain a silicon substrate B8.

[0097] S35: Using a DC magnetron sputtering process, a layer of platinum metal film is sputtered on the front side of the silicon substrate B8, and then it is soaked in acetone and rinsed with deionized water to remove the photoresist to obtain a silicon substrate B9.

[0098] S36: Laser scribing the silicon substrate B9 to obtain a lower wafer.

[0099] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. It should be noted that any modification, equivalent replacement, improvement, etc. made by a person skilled in the art within the spirit and principle of the present invention after reading this specification should be included in the protection scope of the present invention.

Claims

1. A transmission electron microscope electrochemical detection chip, comprising an upper chip and a lower chip, both of which are silicon substrates with insulating layers on both the front and back sides, the front side of the upper chip and the front side of the lower chip are fixedly bonded by an adhesive layer, and the upper chip, the lower chip and the adhesive layer together form a chamber; the upper chip is provided with a sample injection port and a first window, characterized in that: The lower sheet is provided with a working electrode, a reference electrode, a counter electrode, a second viewing window and a thermometer, and the working electrode, the reference electrode and the counter electrode are all arranged on the second viewing window; The working electrode is located in the center of the second viewing window, the counter electrode and the working electrode are arranged side by side on the second viewing window, the reference electrode is arranged perpendicular to the working electrode on the second viewing window, and the thermometer is arranged on the second viewing window and opposite to the counter electrode and the working electrode; the tip of the working electrode is all on the second viewing window, and the narrowest part of the tip of the working electrode is 3 to 15 microns; the thermometer is a regular square wave shape composed of a platinum metal film pattern; It also includes a carbon electrode, which covers the working electrode and is not in contact with the counter electrode; the carbon electrode is composed of a carbon film plated on the working electrode.

2. A method for manufacturing a transmission electron microscope electrochemical detection chip, characterized in that: include: S1: Processing a sample injection port and a first window on a silicon substrate A provided with insulating layers on both the front and back sides to manufacture an upper wafer; S2: A working electrode, a reference electrode, a counter electrode, a second window and a thermometer are processed on a silicon substrate B provided with insulating layers on both the front and back sides to manufacture a lower wafer; Wherein, step S2 comprises: S21: using a photolithography process, transferring the second window pattern from the photolithography mask to the back side of the silicon substrate B having an insulating layer on both the front and back sides, developing in a positive photoresist developer, and rinsing with deionized water to obtain a silicon substrate B1; S22: using a reactive ion etching process to remove the insulating layer on the back side of the silicon substrate B1 corresponding to the second window, and then removing the photoresist to obtain a silicon substrate B2; S23: using a wet etching process to remove the base silicon of the silicon substrate B2 and the second window, and then washing with deionized water to obtain a silicon substrate B3; S24: using a photolithography process, transferring the working electrode, reference electrode and counter electrode patterns from the photolithography mask to the front side of the silicon substrate B3, developing in a positive photoresist developer, and rinsing with deionized water to obtain a silicon substrate B4; S25: using a DC magnetron sputtering process, a layer of electrode material film is sputtered on the front side of the silicon substrate B4, and then soaked in acetone, rinsed with deionized water, and the photoresist is removed to obtain a silicon substrate B5; S26: using a photolithography process, transferring the thermometer pattern from the photolithography mask to the front side of the silicon substrate B5, developing it in a positive photoresist developer, and rinsing it with deionized water to obtain a silicon substrate B6; S27: Using a DC magnetron sputtering process, a layer of platinum metal film is sputtered on the front of the silicon substrate B6, and then the silicon substrate B6 is soaked in acetone and rinsed with deionized water to remove the photoresist, thereby obtaining a silicon substrate B7; S28: Laser scribing the silicon substrate B7 to obtain a lower wafer; S3: The upper sheet and the lower sheet are fixedly bonded by an adhesive layer to obtain a transmission electron microscope electrochemical detection chip.

3. The method for manufacturing a transmission electron microscope electrochemical detection chip according to claim 2, characterized in that: Replace steps S26 to S28 with: S31: Using radio frequency magnetron sputtering technology, a carbon film is sputtered on the front side of the silicon substrate B5; S32: using a photolithography process to transfer the carbon electrode pattern from the photolithography mask to the front side of the silicon substrate B5, and then using a reactive ion etcher to remove the carbon film not protected by the photoresist to obtain a silicon substrate B6'; S33: removing the photoresist to obtain a silicon substrate B7'; S34: using a photolithography process, transferring the thermometer pattern from the photolithography mask to the front side of the silicon substrate B7', developing it in a positive photoresist developer, and cleaning the surface with deionized water to obtain a silicon substrate B8; S35: using a DC magnetron sputtering process, sputtering a layer of platinum metal film on the front side of the silicon substrate B8, soaking it in acetone, rinsing it with deionized water, removing the photoresist, and obtaining a silicon substrate B9; S36: Laser scribing the silicon substrate B9 to obtain a lower wafer.

4. The method for manufacturing a transmission electron microscope electrochemical detection chip according to claim 2, characterized in that: The photolithography process used in step S21 is: exposure in the hard contact mode of the ultraviolet photolithography machine, the development time is 60 seconds, and the exposure time is 15 seconds.

5. The method for manufacturing a transmission electron microscope electrochemical detection chip according to claim 2, characterized in that: The wet etching process adopted in step S23 is: etching with a potassium hydroxide solution having a mass percentage concentration of 20%, an etching temperature of 80° C., and an etching time of 2 hours.

6. The method for manufacturing a transmission electron microscope electrochemical detection chip according to claim 3, characterized in that: Step S32 includes: etching the carbon film not protected by the photoresist in argon and oxygen, with an etching power of 50 watts and an etching time of 30 seconds.

Images