阅读说明：本技术 一种电化学测量微电极结构及其制作方法 (Electrochemical measurement microelectrode structure and manufacturing method thereof ) 是由 胡一帆 宋航 丁显波 赵鑫 于 2021-08-25 设计创作，主要内容包括：本发明公开一种电化学测量微电极结构及其制作方法,该微电极结构包括：绝缘基底、电极、导电线和绝缘保护层,所述电极和所述导电线设于所述绝缘基底的上方,所述电极和所述导电线相连接,所述绝缘保护层覆盖于所述电极和所述导电线上方；所述绝缘基底上设有若干不连续的空孔,所述若干空孔对应所述电极的位置设置,每一所述空孔均连通至所述电极,其中一个空孔或多个空孔内形成近电极控制部。本发明的电化学测量微电极结构能按需灵活定制微电极电极有效尺度,并维持电极露于空孔或近电极控制部中的材料表面特征,实现微电极的更广泛的材质选用和更丰富的表面状态。本发明的电化学测量微电极结构设计灵活,制作方法易于构建,易于批量生产。(The invention discloses an electrochemical measurement microelectrode structure and a manufacturing method thereof, wherein the microelectrode structure comprises the following components: the electrode and the conductive wire are arranged above the insulating substrate and are connected, and the insulating protective layer covers the electrode and the conductive wire; the insulating substrate is provided with a plurality of discontinuous holes, the plurality of holes are arranged corresponding to the positions of the electrodes, each hole is communicated to the electrodes, and a near electrode control part is formed in one hole or a plurality of holes. The electrochemical measurement microelectrode structure can flexibly customize the effective dimension of the microelectrode electrode according to the requirement, maintain the surface characteristics of the material of the electrode exposed in the hollow hole or the near electrode control part, and realize wider material selection and richer surface state of the microelectrode. The electrochemical measurement microelectrode of the invention has flexible structure design, easy construction of the manufacturing method and easy batch production.)

1. An electrochemical measurement microelectrode structure, comprising: the electrode and the conductive wire are arranged above the insulating substrate and are connected, and the insulating protective layer covers the electrode and the conductive wire; the insulating substrate is provided with a plurality of discontinuous holes, the plurality of holes are arranged corresponding to the positions of the electrodes, each hole is communicated to the electrodes, and a near electrode control part is formed in one hole or a plurality of holes.

2. The electrochemical measurement microelectrode structure of claim 1, wherein the proximal electrode control unit is formed by filling the hollow pores with a substance or by surface-treating the inner surfaces of the hollow pores.

3. The electrochemical measurement microelectrode structure of claim 2, wherein the substance fill comprises: resin filling or powder filling; the surface treatment comprises: plasma sputtering, chemical etching, chemical grafting or electrochemical deposition.

4. The electrochemical measurement microelectrode structure of any of claims 1 to 3, wherein the insulating substrate has a thickness of 10um to 10mm and the width of the cavity is 0.1 μm to 1 mm.

5. The electrochemical measurement microelectrode structure of claim 4, wherein the electrode is made of conductive paste, graphene, carbon nanotubes, metal flakes or semiconductor material.

6. A method of making an electrochemical measurement microelectrode structure according to any of claims 1 to 5, comprising the steps of:

s10, providing an insulating substrate, and forming a conductive line on the insulating substrate;

s20, forming a plurality of discontinuous holes on the insulating substrate, wherein each hole penetrates through the thickness of the insulating substrate;

s30, attaching electrodes above the holes, and connecting the electrodes with the conducting wires;

s40, covering an insulating protective layer above the electrode, the conducting wire and the insulating substrate;

and S50, processing one or more empty holes to form a near electrode control part.

7. The method of fabricating an electrochemical measurement microelectrode structure of claim 6, wherein the step of forming the conductive line in step S10 comprises: printing conductive paste on the insulating substrate; or the conductive metal sheet is connected to the insulating substrate in a pressing and/or bonding and fixing mode.

8. The method of fabricating an electrochemical measurement microelectrode structure of claim 6, wherein the forming of the cavity in step S20 comprises: mechanical drilling, laser drilling, radiation bombardment, or chemical reaction to the hole.

9. The method of manufacturing an electrochemical measurement microelectrode structure of claim 6, wherein the step S30 includes: thermal compression, UV resin curing or resin thermal curing.

10. The method of fabricating an electrochemical measurement microelectrode structure of claim 6, wherein the step S40 includes the steps of: and coating insulating slurry or attaching an insulating film on the electrodes, the conductive wires and the insulating substrate.

Technical Field

The invention relates to the technical field of electrochemical measurement electrodes, in particular to an electrochemical measurement microelectrode structure and a manufacturing method thereof.

Background

The micro-electrode means: the geometry of the electrodes is at least one dimension on the order of microns, and typically the electrodes are encapsulated in an insulating material such as a thermosetting resin with a diameter of a few microns, and the resin tips are polished to expose the electrode surfaces.

The characteristics of this type of electrode are:

(1) the passing current is small, and the electrolyte solution can be used for high internal resistance (low conductance);

(2) the electrode has small size and can be used for analyzing and measuring substances with micro volume;

(3) as the measurement time increased, the diffusion process changed from linear to spherical diffusion.

These characteristics make microelectrodes suitable for the precise measurement study of detailed processes of electrochemical reactions. The application of the method can improve the detection limit of point analysis and measurement and is suitable for wider electrolyte solutions. If the microelectrode is arranged on a functional device with three-dimensional movement and positioning, a scanning electrochemical microscope can be constructed, and the electrochemical reaction state and the process of a surface micro-area can be researched.

The conventional microelectrode is usually a metal wire as the electrode conducting part, and the insulating part of the outer cover can be a high molecular material such as thermosetting resin or an inorganic non-metallic material such as glass and the like. The construction method of the microelectrode is limited by conductive materials and interface conditions thereof, has little change, is not flexible enough, has few reaction types, and can not fully meet the detection requirement of specialization and simplification under specific scenes.

Therefore, constructing a microelectrode which can flexibly customize the effective dimension of the microelectrode electrode according to the requirement, so that the microelectrode has wider material selection and richer surface states to realize the design and control of a diffusion channel of a specific substance in a measured object system is a technical problem to be solved urgently by technical personnel in the field.

Disclosure of Invention

In order to solve the technical problems, the invention provides an electrochemical measurement microelectrode structure and a manufacturing method thereof. The method changes the conventional method for controlling the diameter of a metal wire or a carbon rod, and realizes the control of the effective dimension of the microelectrode electrode. The technical scheme of the invention is as follows:

first, the present invention provides an electrochemical measurement microelectrode structure comprising: the electrode and the conductive wire are arranged above the insulating substrate and are connected, and the insulating protective layer covers the electrode and the conductive wire; the insulating substrate is provided with a plurality of discontinuous holes, the plurality of holes are arranged corresponding to the positions of the electrodes, each hole is communicated to the electrodes, and a near electrode control part is formed in one hole or a plurality of holes.

Further, the near electrode control portion is formed by filling a substance into the hollow hole or by performing surface treatment on the inner surface of the hollow hole.

Further, the substance filling includes: resin filling or powder filling; the surface treatment comprises: plasma sputtering, chemical etching, chemical grafting or electrochemical deposition.

Further, the thickness of the insulating substrate is 10um-10mm, and the width of the hollow hole is 0.1 μm-1 mm.

Further, the electrode is made of conductive paste, graphene, carbon nanotubes, metal sheets or semiconductor materials.

Secondly, the invention also provides a manufacturing method of the electrochemical measurement microelectrode structure, which comprises the following steps:

s10, providing an insulating substrate, and forming a conductive line on the insulating substrate;

s20, forming a plurality of discontinuous holes on the insulating substrate, wherein each hole penetrates through the thickness of the insulating substrate;

s30, attaching electrodes above the insulating substrate corresponding to the plurality of holes, and connecting the electrodes with the conducting wires;

s40, covering an insulating protection layer above the electrode and the conducting wire;

and S50, processing one or more empty holes to form a near electrode control part.

Further, the method of forming the conductive line in step S10 includes: printing conductive paste on the insulating substrate; or the conductive metal sheet is connected to the insulating substrate in a pressing and/or bonding and fixing mode.

Further, in step S20, the method for forming the void includes: mechanical drilling, laser drilling, radiation bombardment, or chemical reaction to the hole.

Further, in step S30, the method for bonding an electrode includes: thermal compression, UV resin curing or resin thermal curing.

Further, in step S40, the method for forming the insulating protection layer includes: and coating insulating slurry or attaching an insulating film on the electrodes, the conductive wires and the insulating substrate.

By adopting the scheme, the invention provides an electrochemical measurement microelectrode structure and a manufacturing method thereof, and the electrochemical measurement microelectrode structure has the following beneficial effects:

(1) the effective dimension of the microelectrode electrode can be flexibly customized according to the requirement, the surface characteristics of the material of the electrode exposed in the hollow hole or the near electrode control part are maintained, and the wider material selection and richer surface state of the microelectrode are realized.

(2) And further, the design and the control of a diffusion channel of a specific substance in a system to be measured are realized by controlling the thickness of the insulating substrate, the size of the hollow hole, the composition of the electrode and the surface state.

(3) The microelectrode is flexible in design, easy to construct in a manufacturing method and easy to produce in batches.

Drawings

FIG. 1 is a schematic sectional view of a structure of an electrochemical measuring microelectrode of the present invention.

Detailed Description

The invention is described in detail below with reference to the figures and the specific embodiments.

As shown in FIG. 1, which is a schematic sectional view of a structure of an electrochemical measurement microelectrode of the present invention, it can be seen that it comprises: the structure comprises an insulating substrate 10, electrodes 20, a conductive wire 30 and an insulating protective layer 40, wherein the insulating substrate 10 is an insulating film which can be PET, PE, PC, a thin glass sheet, an oxidized wafer silicon sheet and the like, and the thickness of the insulating film is controlled to be 10 mu m-10mm so as to control the distance of a diffusion channel or control the thickness of a filler and ensure the rigidity of the electrodes.

The electrode 20 and the conductive line 30 are disposed above the insulating substrate 10, and the electrode 20 and the conductive line 30 are connected. The electrode 20 and the conductive wire 30 may be of an integral structure or of different structures and electrically connected together. The electrode 20 may be made of conductive paste, graphene, carbon nanotubes, metal sheets, semiconductor materials, etc., and is set according to a detection scenario and a detection requirement, for example, when a response current is large (at milliampere level or above), a test is performed on the metal sheets, and a hydrophobic interface may be selected from a specific class of carbon-based materials. The conductive line 30 may be a printed or coated conductive paste, a conductive film deposited by PVD or CVD, or the like, for connecting the electrode 20 to a measuring instrument, typically a measuring instrument such as an electrochemical workstation or potentiostat, or the like.

The insulating protection layer 40 covers the electrodes 20 and the conductive wires 30, and is tightly attached to the insulating substrate 10 to prevent other substances such as electrolyte components from entering the interface. The insulating protective layer 40 may be an insulating paste printed or coated on the surfaces of the electrode 20 and the conductive line 30, or an insulating film attached to the surfaces of the electrode 20 and the conductive line 30, and has a thickness controlled between 0.1 μm and 1mm, and a width greater than that of the electrode 20, and completely covers the electrode 20 and the conductive line 30 without exposing the same.

A plurality of discontinuous holes 11 are formed in the bottom of the insulating substrate 10, the plurality of holes 11 are arranged at positions corresponding to the electrodes 20, and each hole 11 penetrates through the thickness of the insulating substrate 10 and is communicated with the electrode 20. Wherein the proximal electrode control portion 12 is formed in one or more of the voids. The holes 11 can be round holes, square holes or holes in any shape, and the forming method of the holes can be mechanical drilling, laser drilling, radiation bombardment, chemical reaction to holes and the like. The width of each void may be set according to the characteristics of the substance to be detected, and preferably, the void is a circular hole having a diameter of 10nm to 10 mm.

The near electrode controller 12 is formed by filling the inside of the hollow hole 11 with a substance or by surface-treating the inner surface of the hollow hole 11. Wherein the substance filling comprises: resin filling or powder filling, the kind of resin or powder is set according to the characteristics of the substance to be measured, such as: when the specific adsorption performance of a certain resin needs to be researched or the influence of the specific adsorption performance on the diffusion coefficient of the electrolyte needs to be researched, the resin can be filled into the hollow hole 11, and the characterization or the measurement can be carried out by measuring the change of the response parameters of the electrode before and after filling. The inner surface treatment comprises forming a layer of corresponding nanoparticles on the exposed electrode 20 in the hollow hole 11 by plasma sputtering, chemical etching, chemical grafting or electrochemical deposition, and then detecting the catalytic performance. Similarly, different surface treatment methods can be selected for different detection scenes and detection conditions, such as: when researching the catalytic performance of a certain kind of electrodeposited nano-metal, the metal nano-particles need to be electrodeposited on the electrode 20 leaking from the bottom surface of the hollow hole 11, and then the catalytic performance of the metal nano-particles is detected.

It should be noted that, the connection parts between the insulating substrate 10 and the conductive wire 30, between the conductive wire 30 and the insulating protection layer 40, between the insulating substrate 10 and the electrode 20, and between the insulating protection layer 40 and the electrode 20 are tightly connected in a seamless manner, which can prevent other substances such as electrolyte components from entering the connection interface, and the bonding ability between the layers can depend on the material itself, such as printing paste of contained resin, organic matter hot-pressing bonding, or can be through another bonding material, such as spin coating or printing bonding layer. The measuring object and the interferent can only contact with the electrode 20 through the hollow hole 11 or the near electrode control part 12, interface effect or electrochemical reaction occurs, and a measuring signal is generated and transmitted to the measuring instrument through the conducting wire 30, and the detection value is read.

The invention also provides a manufacturing method of the electrochemical measurement microelectrode structure, which comprises the following steps:

s10, providing an insulating substrate 10, wherein the insulating substrate 10 is an insulating film, which can be PET, PE, PC thin glass sheet, oxidized silicon wafer, etc., and the thickness thereof is controlled to be 10 μm-10 mm. And forming a conductive line 30 on the insulating substrate 10, the conductive line 30 being formed on the insulating substrate 10 by printing a conductive paste; or, the conductive metal sheet is rigidly connected to the insulating substrate 10 by pressing or bonding to form the conductive wire 30.

S20, forming a plurality of discontinuous holes 11 on the insulating substrate 10, wherein the method for forming the holes 11 includes: mechanical drilling, laser drilling, radiation bombardment or chemical reaction to a hole, etc. Each of the voids 11 extends through the thickness of the insulating substrate 10.

S30, attaching an electrode 20 on the insulating substrate 10 corresponding to the plurality of holes 11, wherein the attaching method of the electrode 20 includes: thermal compression, UV resin curing or resin thermal curing. The electrode 20 and the conductive wire 30 are electrically connected together, and the electrode 20 and the conductive wire 30 may be an integral structure made of the same material or may be electrically connected together and made of different materials. The electrode 20 may be made of conductive paste, graphene, carbon nanotubes, metal sheets, semiconductor materials, or the like. The conductive line 30 may be a printed or coated conductive paste, a conductive thin film deposited by PVD or CVD, etc., and the conductive line 30 is used to connect the electrode 20 and the measuring instrument.

S40, covering an insulating protective layer 40 over the electrodes 20 and the conductive lines 30. The insulating protective layer 40 may be an insulating paste or an insulating film printed or coated on the electrode 20, the conductive line 30 and the insulating substrate 10, or may be an insulating film attached to the electrode 20, the conductive line 30 and the insulating substrate 10. The insulating protective layer 40 is used to cover the electrode 20 and the conductive line 30, and is tightly combined with the insulating substrate 10 to form an insulating protection for the electrode 20 and the conductive line 30.

S50, processing one or more of the holes 11 to form a proximal electrode control part 12. The treatment comprises a substance filling or an internal surface treatment, wherein the substance filling comprises: resin filling or powder filling, and the type of resin or powder is set according to the characteristics of the substance to be measured. The inner surface treatment includes forming a layer of metal nanoparticles on the exposed electrode 20 in the cavity 11 by plasma sputtering, chemical etching, chemical grafting or electrochemical deposition, etc. Similarly, different interior surface treatment methods may be selected for different inspection scenarios and inspection conditions. The arrangement of the near electrode control part 12 is relatively only provided with the hollow hole 11, so that the defect that the exposed part of the hollow hole 11 is directly contacted with the test solution can be overcome, more various substance layers are superposed, and more abundant measurement functions are realized. For example: the method comprises the steps of filtering large particle substances of a test solution, replacing specific cations or anions, providing reaction substrates for certain chemical reactions, and adjusting the diffusion coefficient of the reaction substrates or products so as to control thermodynamic parameters of the reactions to a certain degree.

The electrochemical measurement microelectrode structure and the manufacturing method thereof can flexibly customize the effective dimension of the microelectrode electrode according to the requirement, maintain the surface characteristics of the material of the electrode exposed in the hollow hole or the near electrode control part, and realize wider material selection and richer surface state of the microelectrode. The electrochemical measurement microelectrode disclosed by the invention is flexible in structural design, easy to construct and easy to produce in batches, and is worthy of being widely popularized and used.

The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.