In-situ transmission electron microscope electrical liquid chip and preparation method thereof

Abstract

The application relates to the field of in-situ transmission electron microscopy, and provides an in-situ transmission electron microscopy electrical liquid chip and a preparation method thereof. The in-situ transmission electron microscopy electrical liquid chip comprises a functional chip, a cover plate chip and a cover plate. The functional chip comprises a first substrate, a first thin film supporting layer and a metal electrode layer, the metal electrode layer comprises a working electrode, a counter electrode and a reference electrode lead wire, and a passivation protective layer partially covers the first thin film supporting layer and the metal electrode layer. The cover plate chip comprises a second substrate and a second thin film supporting layer. The cover plate is arranged on the top of the functional chip and covers a liquid storage groove. The in-situ transmission electron microscopy electrical liquid chip and the preparation method thereof provided by the application introduce a three-electrode test system in the traditional electrochemistry field into a transmission electron microscope on the basis of realizing liquid environment application, can realize atomic scale in-situ dynamic observation of electrochemical behaviors of samples in a liquid environment, and can realize accurate control and collection of electrical signals.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of in-situ transmission electron microscopy high-resolution in-situ characterization technology, and particularly relates to an in-situ transmission electron microscopy electric liquid chip and a preparation method thereof. BACKGROUND

[0002] Liquid is one of the basic states of matter in nature. Liquid environment is also an important place for various chemical and physical reactions in the fields of material science and life science. Studying the microstructure changes of different materials in liquid environment can help us understand the essential characteristics of materials more comprehensively and objectively, and then guide the design of various new high-performance materials. Liquid transmission electron microscopy (LPTEM) has developed rapidly in recent years due to the strong demand for functional materials. By applying the high spatial resolution, structure analysis and composition analysis functions of transmission electron microscopy to the imaging and analysis of liquid samples (especially high vapor pressure liquids such as water), the dynamic process of microstructure evolution in liquid environment can be observed, which cannot be observed by traditional static microscopic analysis methods.

[0003] In the prior art, in-situ MEMS liquid chips and sample rods for transmission electron microscopy have been developed. Some of them have metal contacts integrated at the front end of the in-situ liquid sample rod. By connecting these metal contacts with the metal electrodes on the electrochemical liquid chip, the control and collection of TEM liquid experiment electrical signals can be completed. Some designs a liquid chip for TEM in-situ liquid experiment under electric field, and designs three platinum metal current-carrying electrodes (working electrode, counter electrode and reference electrode) on the surface of the chip, which can meet the measurement needs of more accurate electrochemical experiments such as electrochemical impedance spectroscopy, cyclic voltammetry curve, battery charging and discharging curve. Some designs a layer of metal resistance wire on the surface of the TEM in-situ liquid chip according to the needs of liquid experiment electric field loading, which can be used for electric field loading and measurement (three-electrode design: working electrode, counter electrode, reference electrode).

[0004] But the above several transmission electron microscope electrical liquid chip has the common problem, namely its used three electrode test system in the working electrode, the counter electrode, the reference electrode material is same, the structure is simple, its reference electrode belongs to the pseudo reference electrode, and the requirement does not comply with electrochemical three electrode test system. The reference electrode in the electrochemical three electrode test system needs to have the electrolyte solution corresponding to the selected reference electrode in the use process in addition to selecting the appropriate reference electrode material according to the reaction system. The corresponding electrolyte solution that the reference electrode extends into and the electrolyte solution required for the electrochemical reaction of the working electrode are two different electrolyte solutions, and the two electrolyte solutions need to be placed in two separated liquid pools to avoid cross contamination between the solutions. But in the process of electrochemical reaction, ion exchange of two kinds of electrolyte solution occurs, the working electrode and the reference electrode are connected to form a measurement control loop, and the change of the electrical signal in the process of electrochemical reaction on the working electrode (the measurement control loop formed by the working electrode and the reference electrode does not have a polarization current flowing in the working process, only a small measurement current exists). SUMMARY

[0005] The application provides an in-situ transmission electron microscope electrical liquid chip and a preparation method thereof, breaks through the limitation of the narrow pole piece space size and high vacuum environment of the transmission electron microscope, introduces the three-electrode test system in the traditional electrochemistry field into the transmission electron microscope on the basis of realizing the application of the liquid environment. The chip can perform atomic-scale in-situ dynamic observation on the electrochemical behavior of the sample in the liquid environment, and complete accurate control and collection of electrical signals.

[0006] The application provides an in-situ transmission electron microscope electrical liquid chip, which is arranged on a sample rod of a transmission electron microscope and comprises a functional chip, a cover chip and a cover plate.

[0007] The functional chip comprises:

[0008] A first base is provided with at least one first through hole, and a liquid storage groove is arranged on the top of the first base;

[0009] A first thin film bearing layer is arranged on the top of the first base;

[0010] A metal electrode layer is arranged on the top of the first thin film bearing layer and comprises a working electrode, a counter electrode and a reference electrode lead wire; the front end of the working electrode extends to the first range of one of the first through holes; and the lead wire of the reference electrode extends into the liquid storage groove;

[0011] A passivation protective layer partially covers the first thin film bearing layer and the metal electrode layer; the uncovered part is a sample reaction area or an external lead wire area;

[0012] The cover chip comprises:

[0013] A second substrate is arranged on the top of the passivation protective layer and covers the front ends of the working electrode, the counter electrode and the reference electrode, but does not cover the liquid reservoir; the second substrate is provided with a second through hole corresponding to the first through hole;

[0014] A second thin film bearing layer is arranged on the side of the second substrate close to the passivation protective layer;

[0015] The cover plate is arranged on the top of the functional chip, and the cover plate covers the liquid reservoir.

[0016] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the first substrate is provided with a plurality of first through holes, and the top of at least one first through hole is suspended and covered by the first thin film bearing layer.

[0017] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the first substrate is further provided with a strip-shaped groove in communication with the liquid reservoir, and the strip-shaped groove is arranged in parallel with the front end of the working electrode.

[0018] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the first thin film bearing layer and the second thin film bearing layer are one of silicon nitride, silicon oxide, silicon carbide, graphene, graphene oxide and boron nitride.

[0019] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the front ends of the working electrode and the counter electrode are both symmetric axis patterns, and the symmetric axes of the two are coaxial.

[0020] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the front end of the counter electrode is arranged in a fishtail number structure, and one side of the semicircle is close to the working electrode.

[0021] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the front end of the working electrode extends to the center of the first through hole, is close to the first through hole, or penetrates from one side of the first through hole to the other side of the first through hole.

[0022] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the metal electrode further comprises a registration mark, and the edge of the cover plate chip coincides with the registration mark.

[0023] According to the in-situ transmission electron microscope electrical liquid chip provided by the application, the lead wire of the reference electrode is arranged at the edge of the liquid reservoir, and the lead wire of the reference electrode is away from the front ends of the working electrode and the counter electrode.

[0024] The application further provides a preparation method of the in-situ transmission electron microscope electrical liquid chip, which comprises the following steps:

[0025] Prepare and clean the single wafer A to ensure that organic matter and metal ion contaminants are removed before high temperature processing;

[0026] Etch a reservoir on the base of the single wafer A by a wet etching process or a reactive ion etching process to obtain a wafer A1;

[0027] Grow a first thin film carrier layer on the surface of the wafer A1 to obtain a wafer A2;

[0028] Grow a metal electrode layer on the surface of the wafer A2, and form working electrode, counter electrode, reference electrode lead and counter mark by an etching process or a stripping process to obtain a wafer A3;

[0029] Grow a passivation protective layer on the surface of the wafer A3 to obtain a wafer A4;

[0030] Pattern the passivation protective layer by an etching process or a stripping process to obtain a wafer A5;

[0031] Etch the wafer A5 from the back by an etching process to form a first through hole to obtain a wafer A6;

[0032] Dicing the wafer A6 to obtain a chip.

[0033] The in-situ transmission electron microscope electrical liquid chip provided by the application has the reservoir arranged on the top of the first base, and the lead of the reference electrode extends to the edge of the reservoir; the second base is arranged on the top of the passivation protective layer, covers the front end of the working electrode and the front end of the counter electrode, partially covers the strip-shaped groove parallel to the working electrode, and does not cover the reservoir; the electrolyte solution into which the reference electrode extends can be effectively distinguished and isolated from the electrolyte solution required for the electrochemical reaction of the working electrode, so that the use requirements of the reference electrode and the corresponding electrolyte solution of different electrochemical reaction systems in different in-situ liquid experiments of the transmission electron microscope are met.

[0034] Moreover, the arrangement of the passivation protective layer can protect the metal electrode not participating in the electrochemical reaction and improve the measurement and control precision of the electrical signal in the in-situ liquid experiment; on the other hand, the layer height of the reaction liquid pool in the in-situ liquid experiment is effectively controlled, that is, the solution amount of the reaction liquid pool is controlled. BRIEF DESCRIPTION OF DRAWINGS

[0035] In order to more clearly illustrate the technical solutions in the application or prior art, the following will briefly introduce the drawings needed to be used in the embodiments or prior art description. Obviously, the drawings in the following description are some embodiments of the application, and other drawings can also be obtained by those skilled in the art without creative effort.

[0036] Figure 1is a structural schematic diagram of an in-situ transmission electron microscope electric liquid chip provided by the present application;

[0037] Figure 2 is a structural schematic diagram of a first substrate and a first film layer in a functional chip provided by the present application;

[0038] Figure 3 is a structural schematic diagram of a first substrate, a first film layer and a metal electrode layer in a functional chip provided by the present application;

[0039] Figure 4 is a structural schematic diagram of a first substrate, a first film layer, a metal electrode layer and a passivation protective layer in a functional chip provided by the present application;

[0040] Figure 5 is a partial enlarged schematic diagram of a metal electrode layer provided by the present application;

[0041] Figure 6 is a structural schematic diagram of a cover chip provided by the present application;

[0042] Reference signs:

[0043] 1, functional chip; 11, first substrate; 12, liquid storage groove; 13, first film bearing layer; 14, metal electrode layer; 141, working electrode; 142, counter electrode; 143, reference electrode lead; 144, counter mark; 15, passivation protective layer; 16, first through hole; 17, strip-shaped groove;

[0044] 2, cover chip; 21, second substrate; 22, second film bearing layer; 23, second through hole;

[0045] 3, cover. DETAILED DESCRIPTION

[0046] In order to make the objectives, technical solutions and advantages of the present application clearer, the technical solutions in the present application will be described clearly and completely below in combination with the drawings in the present application. Obviously, the described embodiments are some of the embodiments of the present application, but not all the embodiments. Based on the embodiments in the present application, all the other embodiments obtained by those skilled in the art without any creative work under the premise of the present application, all belong to the scope of protection of the present application.

[0047] In the description of the embodiments of the present application, it should be noted that the terms "center", "longitudinal", "transverse", "upper", "lower", "front", "back", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer" and the like indicate the orientation or positional relationship shown in the drawings, and are only for the convenience of describing the embodiments of the present application and simplifying the description, and do not indicate or imply that the devices or elements referred to must have a particular orientation, be constructed and operated in a particular orientation, and therefore cannot be understood as a limitation on the embodiments of the present application. In addition, the terms "first", "second", "third" are only for the purpose of description, and cannot be understood as indicating or implying relative importance.

[0048] The following will be described in conjunction with Figures 1 to 6 The in-situ transmission electron microscope liquid chip of the present application is arranged on a transmission electron microscope sample rod. As shown in Figure 1 The in-situ transmission electron microscope liquid chip includes a functional chip 1, a cover chip 2 and a cover plate 3. As shown in Figures 1-6 The functional chip 1 includes a first substrate 11, a first thin film support layer 13, a metal electrode layer 14 and a passivation protection layer 15. At least one first through hole 16 is formed in the first substrate 11, and a liquid storage groove 12 and a strip-shaped groove 17 are arranged on the top of the first substrate 11. The first thin film support layer 13 is arranged on the top of the first substrate 11. The metal electrode layer 14 is arranged on the top of the first thin film support layer 13, and includes a working electrode 141, a counter electrode 142 and a reference electrode lead 143. The front end of the working electrode 141 extends to the first range of one of the first through holes 16. The first range here can be understood as the position of the first through hole 16, or the vicinity of the first through hole 16. The reason is that by applying voltage to the working electrode 141 and the counter electrode 142, an electric field exists between the working electrode 141 and the counter electrode 142, and the electric field can cover the first through hole 16, so that the internal situation can be observed through the window formed by the first through hole 16. The reference electrode lead 143 extends to the edge of the liquid storage groove 12. The passivation protection layer 15 partially covers the first thin film support layer 13 and the metal electrode layer 14, and the sample reaction area or the external lead area is not covered by the passivation protection layer 15.

[0049] As Figure 6As shown, the cover chip 2 comprises: a second substrate 21, a second thin film bearing layer 22 and a second through hole 23, the second substrate 21 and the second thin film bearing layer 22 are arranged on the top of the passivation protective layer 15, and the second thin film bearing layer 22 is in contact with the passivation protective layer 15 and covers the working electrode 141, and does not cover the liquid reservoir 12; the second substrate 21 is provided with the second through hole 23 corresponding to the first through hole 16; the second thin film bearing layer 22 is arranged on the side of the second substrate 21 close to the passivation protective layer 15; the cover plate 3 is in the same horizontal plane as the second substrate 21, and the cover plate 3 covers the liquid reservoir 12, the first through hole 16 and the second through hole 23 form an observation window; that is, the cover plate 3 and the cover chip 2 are located in the same plane.

[0050] The in-situ transmission electron microscope electrical liquid chip provided by the application can effectively distinguish and isolate the electrolyte solution into which the reference electrode is inserted from the electrolyte solution required for the electrochemical reaction of the working electrode, meet the use requirements of different reference electrodes and the corresponding electrolyte solutions of different electrochemical reaction systems in different in-situ liquid experiments of a transmission electron microscope.

[0051] Moreover, the passivation protective layer 15 can protect the metal electrode not participating in the electrochemical reaction on one hand, and improve the measurement and control precision of the electrical signal in the in-situ liquid experiment; on the other hand, the passivation protective layer 15 can effectively control the layer height of the reaction liquid pool in the in-situ liquid experiment, that is, control the solution amount of the reaction liquid pool.

[0052] In the embodiment of the application, as shown in Figure 2 and Figure 3 When the first substrate 11 is provided with one first through hole 16, the first thin film bearing layer 13 is suspended on the top of the first through hole 16; when the first substrate 11 can be provided with a plurality of first through holes 16, and the top of at least one first through hole 16 is suspended on the first thin film bearing layer 13. The other first through holes 16 can be used as liquid inlet and outlet to form a liquid circulation function.

[0053] As shown in Figure 2 and Figure 4As shown in the embodiment of the present application, a strip-shaped groove 17 is further arranged on the first substrate 11 and communicates with the liquid storage groove 12, and the strip-shaped groove 17 is arranged in parallel with the working electrode 141. The strip-shaped groove 17 is used to place a salt bridge, which is a solid capable of ion exchange, one end of the salt bridge is connected with the reference electrode electrolyte solution, and the other end is connected with the working electrode electrolyte solution, so as to realize ion exchange. The strip-shaped groove 17 has a width similar to the front end of the working electrode 141, which ensures the normal use of the salt bridge and makes the electric field distribution more uniform, thereby improving the precision of potential measurement. Preferably, the distance between the strip-shaped groove 17 and the working electrode 141 is slightly greater than the width of the strip-shaped groove 17, and the strip-shaped groove 17 cannot be too close to the working electrode 141, otherwise it will have a significant shielding effect on the surface of the electrode and affect the current distribution. Therefore, in order to reduce the liquid junction potential and the solution resistance, and not to produce shielding, the distance between the strip-shaped groove 17 and the working electrode 141 is designed to be slightly greater than the width of the strip-shaped groove 17.

[0054] In the embodiment of the present application, the first thin film bearing layer 13 and the second thin film bearing layer 22 are one of silicon nitride, silicon oxide, silicon carbide, graphene, graphene oxide and boron nitride. The first thin film bearing layer 13 and the second thin film bearing layer 22 are usually amorphous thin films with good electron transmittance, good chemical inertness, high resistance, high mechanical strength, low residual stress, low average atomic number and small molecule impermeability. Preferably, the top of the first substrate 11 and the inside of the electrolyte groove are entirely covered.

[0055] The first thin film bearing layer 13 and the second thin film bearing layer 22 are arranged to ensure that the working electrode electrolyte solution does not leak from the first through hole 16 and the second through hole 23, and to form an observation window at the first through hole 16 and the second through hole 23, which can be observed through the first thin film bearing layer 13 and the second thin film bearing layer 22. In addition, since the use environment is an electron microscope, the working electrolyte solution between the functional chip 1 and the cover chip 2 is at least in an atmosphere environment, while the outside of the chip is in a high vacuum environment, so that the first thin film bearing layer 13 and the second thin film bearing layer 22 are prevented from being deformed due to pressure, and the working electrode electrolyte solution is also sealed in the cavity to prevent leakage into the electron microscope.

[0056] In the embodiment of the present application, as shown in the figure, Figure 5 The front ends of the working electrode 141 and the counter electrode 142 are both axisymmetric figures, and the symmetry axes of the two are coaxial.

[0057] It should be noted that the front ends of the working electrode 141 and the counter electrode 142 can be understood as the ends that participate in the operation, that is, the ends closer to the strip groove 17. Setting the front ends of both the working electrode 141 and the counter electrode 142 as axisymmetric shapes can make the electric field distribution more uniform.

[0058] like Figure 3 As shown, in an embodiment of the present invention, the front end of the counter electrode 142 is configured as a fishtail-shaped structure, with the semi-circular side close to the working electrode 141. Here, the fishtail-shaped structure can be understood as a square structure, with a semi-circular section removed from the front end of the square structure near the working electrode 141. This configuration aims to make the electric field distribution more uniform.

[0059] In embodiments of the present invention, the front end of the working electrode 141 extends to the center of the first through hole 16, is close to the first through hole 16 (but does not extend into the first through hole), or penetrates from one side of the first through hole 16 to the other side. That is, the front end of the working electrode 141 and the first through hole 16 can have the above three relative positional relationships: one is extending to the center of the first through hole 16, another is close to the first through hole 16 but not extending into the first through hole 16, and the third is penetrating from one side of the first through hole 16 to the other side. The reason for this arrangement is that, since the working electrode electrolyte solution is disposed around the first through hole 16, as long as the front end of the working electrode 141 is disposed around the first through hole 16, an electric field of the working electrode can be generated in the first through hole 16, and thus it can be observed at the first through hole 16. When the front end of the working electrode 141 is positioned close to the first through hole 16 but not extending into the first through hole 16, or extends from one side of the first through hole 16 to the other side of the first through hole 16, a larger observation area can be formed at the first through hole 16, providing a better field of view.

[0060] like Figure 3 As shown, in an embodiment of the present invention, the metal electrode layer 14 further includes a alignment mark 144, and the corner of the cover plate chip 2 coincides with the alignment mark 144. Since the size of the first through hole 16 and the second through hole 23 is very small, in the micrometer range, setting the alignment mark 144 makes it easier to align the first through hole 16 and the second through hole 23, facilitating installation and observation. At the same time, the cover plate 3 can also cover the functional chip 1 exposed outside the cover plate chip 2, and the cover plate 3 covers the liquid storage tank 12 exposed outside the cover plate chip, so that the entire in-situ transmission electron microscope electro-liquid chip forms an integral sealed structure.

[0061] In an embodiment of the present invention, the reference electrode wire 143 is disposed at the edge of the liquid storage tank 12, and the reference electrode wire 143 is far away from the front end of the working electrode 141 and the counter electrode 142, so as to make the electric field distribution more uniform.

[0062] Another aspect of the present application is to provide a preparation method of an in-situ transmission electron microscope electric liquid chip, comprising the following steps:

[0063] Preparation and cleaning of a single wafer A to ensure removal of organic matter and metal ion contaminants before high temperature processing;

[0064] Etching a liquid storage tank 12 on the substrate of the single wafer A by a wet etching process or a reactive ion etching process to obtain a wafer A1;

[0065] Growing a first thin film carrier layer 13 on the surface of the wafer A1 to obtain a wafer A2;

[0066] Growing a metal electrode layer 14 on the surface of the wafer A2 to form a working electrode 141, a counter electrode 142, a reference electrode lead 143 and a counter mark 144 by etching process or stripping process to obtain a wafer A3;

[0067] Growing a passivation layer 15 on the surface of the wafer A3 to obtain a wafer A4;

[0068] Patternizing the passivation layer 15 by etching process or stripping process to expose the area needing external circuit and the working area of the working electrode electrolyte solution to obtain a wafer A5;

[0069] Etching the wafer A5 from the back by etching process to form a first through hole 16 to obtain a wafer A6;

[0070] Dicing the wafer A6 to obtain a functional chip 1.

[0071] Preparation and cleaning of a single wafer B to ensure removal of organic matter and metal ion contaminants before high temperature processing;

[0072] Growing a second thin film carrier layer 22 on the surface of the wafer B to obtain a wafer B1;

[0073] Etching the wafer B1 from the back by etching process to form a second through hole 23 to obtain a wafer B2;

[0074] Dicing the wafer B2 to obtain a cover chip 2.

[0075] Preparation and cleaning of a single wafer C to ensure removal of organic matter and metal ion contaminants before high temperature processing;

[0076] Etching the wafer C from the back by etching process to obtain a wafer C1;

[0077] Dicing the wafer C1 to obtain a cover 3.

[0078] The cover plate chip 2 aligns with the counter mark 144 of the functional chip and is attached; the cover plate 3 is arranged on the other side of the cover plate chip 2 and covers the liquid storage groove 12.

[0079] The use process of the in-situ transmission electron microscope electrical liquid chip provided by the application is as follows: the in-situ transmission electron microscope electrical liquid chip is fixed on the chip placing groove at the front end of the transmission electron microscope liquid sample rod by using instant adhesive. The wires are led to the transmission electron microscope sample rod from the tail end of the working electrode, the counter electrode and the reference electrode by ultrasonic welding. The sample is carried on the silicon nitride film observation window by using micro-nano sample processing preparation technology, and the electrolyte solution required by the reference electrode wire 143 in the experiment and the electrolyte solution required by the working electrode 141 to participate in the electrochemical reaction are respectively dropped on the surface of the chip. The cover plate chip 2 and the cover plate 3 are covered and sealed with glue. The transmission electron microscope sample rod is inserted into the transmission electron microscope, and the electron microscope parameters are adjusted to the best observation state. After the sample is stable, a certain current or voltage is applied to the power supply electrode according to the experimental requirements. While the electric field of the sample is accurately controlled, the microstructure evolution of the material is observed in-situ and the physical and chemical properties of the material are measured.

[0080] In the description of the embodiments of the application, it should be noted that, unless otherwise explicitly specified and limited, the terms "connected", "connected" should be understood in a broad sense, for example, it can be fixedly connected, or it can be detachably connected, or integrally connected; it can be mechanically connected, or it can be electrically connected; it can be directly connected, or it can be indirectly connected through an intermediate medium. For those skilled in the art, the specific meaning of the above terms in the embodiments of the application can be understood according to the specific circumstances.

[0081] In the description of the present application, the description of the terms "one embodiment", "some embodiments", "way", "specific way", or "some ways" means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or way are included in at least one embodiment or way of the present application. In the present application, the illustrative description of the above terms is not necessarily for the same embodiment or way. Moreover, the specific features, structures, materials or characteristics described can be combined in any appropriate way in any one or more embodiments or ways. In addition, those skilled in the art can combine and combine the different embodiments or features of different embodiments or ways described in the present application without contradiction.

[0082] It should be pointed out finally that the above embodiments are only used to illustrate the technical solutions of the present application, but not to limit the same; and although the present application has been described in detail with reference to the foregoing embodiments, it should be appreciated by those skilled in the art that the technical solutions recorded in the foregoing embodiments can be modified, or some technical features thereof can be replaced equivalently; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. An in-situ transmission electron microscope (TEM) electro-liquid chip, disposed on a TEM sample holder, characterized in that, include: Functional chip, cover chip, and cover plate; The functional chip includes: The first base has at least one first through hole, and the top of the first base is provided with at least one liquid storage tank and strip groove; A first thin film carrier layer is disposed on top of the first substrate; A metal electrode layer is disposed on top of the first thin film carrier layer, including a working electrode, a counter electrode, and a reference electrode wire; and the front end of the working electrode extends into a first range of one of the first through holes; the first range is the location of the first through hole or the area near the first through hole; the reference electrode wire is disposed at the edge of the liquid storage tank; A passivation protective layer partially covers and wraps the first thin film carrier layer and the metal electrode layer, while the uncovered portion is the sample reaction area or the external wire area. The cover plate chip includes: The second substrate is disposed on top of the passivation protective layer and covers the front ends of the working electrode, counter electrode and reference electrode, partially covers the strip groove, and does not cover the liquid storage tank; a second through hole corresponding to the first through hole is formed on the second substrate; The second thin film carrier layer covers the side of the second substrate near the passivation protective layer; The cover plate is disposed on the top of the functional chip and covers the liquid storage tank; a strip groove communicating with the liquid storage tank is also disposed on the first substrate, and the strip groove is disposed parallel to the front end of the working electrode; the distance between the strip groove and the working electrode is greater than the width of the strip groove.

2. The in-situ transmission electron microscopy electro-liquid chip according to claim 1, characterized in that, The first substrate has a plurality of first through holes, and the top of at least one of the first through holes is suspended and covered by the first thin film carrier layer.

3. The in-situ transmission electron microscopy electro-liquid chip according to claim 1, characterized in that, The first thin film carrier layer and the second thin film carrier layer are one of silicon nitride, silicon oxide, silicon carbide, graphene, graphene oxide, and boron nitride.

4. The in-situ transmission electron microscopy electro-liquid chip according to claim 1, characterized in that, The front ends of both the working electrode and the counter electrode are symmetrical axis shapes, and their symmetrical axes are coaxial.

5. The in-situ transmission electron microscopy electro-liquid chip according to claim 4, characterized in that, The front end of the counter electrode is configured as a fishtail-shaped structure, with one semi-circular side close to the working electrode.

6. The in-situ transmission electron microscopy electro-liquid chip according to claim 4, characterized in that, The front end of the working electrode extends to the center of the first through hole, close to the first through hole, or through one side of the first through hole to the other side of the first through hole.

7. The in-situ transmission electron microscopy electro-liquid chip according to claim 1, characterized in that, The metal electrode also includes a matching mark, and the corner of the cover chip coincides with the matching mark; the through hole of the cover chip covered by the second thin film carrier layer coincides vertically with the through hole of the functional chip covered by the first thin film carrier layer.

8. The in-situ transmission electron microscopy electro-liquid chip according to claim 1, characterized in that, The lead wire of the reference electrode is located away from the front end of the working electrode and the counter electrode.

9. A method for preparing an in-situ transmission electron microscopy (TEM) electro-liquid chip, used to prepare the in-situ TEM electro-liquid chip according to any one of claims 1-8, characterized in that, Includes the following steps: Prepare and clean single-crystal wafer A to ensure the removal of organic and metal ion contaminants before high-temperature processing; A liquid reservoir is etched into the substrate of single wafer A using a wet etching process or a reactive ion etching process to obtain wafer A1. A first thin film carrier layer is grown on the surface of wafer A1 to obtain wafer A2; A metal electrode layer is grown on the surface of wafer A2, and working electrode, counter electrode, reference electrode wire and alignment mark are formed by etching process or stripping process to obtain wafer A3; A passivation protective layer is grown on the surface of wafer A3 to obtain wafer A4; The passivation protective layer is patterned using an etching process or a stripping process to obtain wafer A5; The first through-hole is formed by etching wafer A5 from the back side using an etching process, resulting in wafer A6. The wafer A6 is diced to obtain the chip.

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