CN115094371B

CN115094371B - Electrode, preparation method thereof and electronic equipment

Info

Publication number: CN115094371B
Application number: CN202210702370.4A
Authority: CN
Inventors: 吴志威; 周滔; 张玲; 吴英超; 曾子敬
Original assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd; Nanjing Vocational University of Industry Technology NUIT
Current assignee: Guangdong Oppo Mobile Telecommunications Corp Ltd; Nanjing Vocational University of Industry Technology NUIT
Priority date: 2022-06-20
Filing date: 2022-06-20
Publication date: 2024-04-26
Anticipated expiration: 2042-06-20
Also published as: CN115094371A

Abstract

The application provides an electrode, which comprises a priming layer, a transition layer and a silicon carbide chromium nitride layer which are sequentially laminated, wherein the material of the transition layer comprises at least one of silicon nitride chromium and chromium nitride, the surface of the silicon carbide chromium nitride layer far away from the transition layer is provided with a plurality of dents, and the dents are intersected to form a dermatoglyph texture. The silicon chromium carbonitride layer can generate a continuous coupling interface with the skin, improves the contact interface between the electrode and the skin, enables sweat to form a continuous electrolyte membrane between the electrode and the skin, further reduces the contact impedance between the electrode and the skin, and is beneficial to the use of the electrode. The application also provides a preparation method of the electrode and electronic equipment.

Description

Electrode, preparation method thereof and electronic equipment

Technical Field

The application belongs to the technical field of electronic products, and particularly relates to an electrode, a preparation method thereof and electronic equipment.

Background

With the continuous development of technology, electronic devices such as smart watches and smart bracelets are endless, and more electronic devices have the function of detecting various physiological parameters such as heart rate, blood oxygen, sleep, pressure and the like of users. However, in the current detection process, the contact impedance between the electronic equipment and the skin of the user is large, so that the noise of the detection signal is large, and the accuracy of the detection result is affected.

Disclosure of Invention

In view of this, the present application provides an electrode, a method of manufacturing the same, and an electronic device.

In a first aspect, the application provides an electrode, which comprises a priming layer, a transition layer and a silicon chromium carbonitride layer which are sequentially stacked, wherein the material of the transition layer comprises at least one of silicon chromium nitride and chromium nitride, the surface of the silicon chromium carbonitride layer, which is far away from the transition layer, is provided with a plurality of dents, and the dents are intersected to form a dermatoglyph texture.

In a second aspect, the present application provides a method for preparing an electrode, comprising: and forming a priming layer, a transition layer and a silicon chromium carbonitride layer by a deposition method, wherein the priming layer, the transition layer and the silicon chromium carbonitride layer are sequentially laminated, the material of the transition layer comprises at least one of silicon chromium nitride and chromium nitride, the surface of the silicon chromium carbonitride layer far away from the transition layer is provided with a plurality of dents, and the dents are intersected to form a dermatoglyph texture to obtain the electrode.

In a third aspect, the application provides an electronic device, which comprises an electronic device main body, wherein the electronic device main body comprises an electrode, the electrode comprises a priming layer, a transition layer and a silicon chromium carbonitride layer which are sequentially stacked, the material of the transition layer comprises at least one of silicon chromium nitride and chromium nitride, the surface of the silicon chromium carbonitride layer, which is far away from the transition layer, is provided with a plurality of dents, and the dents are intersected to form a dermatoglyph texture.

The surface of the silicon carbide chromium nitride layer far away from the transition layer is provided with a plurality of crossed dents, so that the surface of the silicon carbide chromium nitride layer presents dermatoglyph textures, a continuous coupling interface is generated between the silicon carbide chromium nitride layer and the skin, the contact interface between the electrode and the skin is improved, sweat forms a continuous electrolyte membrane between the electrode and the skin, the contact impedance between the electrode and the skin is further reduced, and the stability and the reliability of the electrode structure are ensured by the arrangement of the bottom layer and the transition layer; the preparation method of the electrode is simple, convenient to operate and high in preparation yield; the electronic equipment with the electrode can detect the physiological parameters of the target object, the electronic equipment can be well contacted with the skin of the target object, the contact impedance is reduced, the detection noise is reduced, the accuracy of the detection result is ensured, and the use of the electronic equipment is facilitated.

Drawings

In order to more clearly explain the technical solutions in the embodiments of the present application, the drawings that are used in the embodiments of the present application will be described below.

Fig. 1 is a schematic structural diagram of an electronic device according to an embodiment of the present application.

Fig. 2 is a schematic structural diagram of an electronic device according to another embodiment of the present application.

Fig. 3 is a schematic structural diagram of an electronic device main body according to an embodiment of the present application.

Fig. 4 is a schematic cross-sectional view of A-A in fig. 3.

Fig. 5 is a schematic cross-sectional view of an electrode according to an embodiment of the present application.

Fig. 6 is an enlarged view of the dotted area in fig. 5.

Fig. 7 is a flowchart of a method for manufacturing an electrode according to an embodiment of the present application.

Fig. 8 is a flowchart of a method for manufacturing an electronic device main body according to an embodiment of the present application.

FIG. 9 is an X-ray diffraction pattern of a silicon chromium carbonitride layer in an electrode obtained in example 1.

FIG. 10 is an electron micrograph of the surface morphology of the SiCrcarbonitride layer in the electrode prepared in example 1.

FIG. 11 is an electron microscopic view of a cross section of the electrode obtained in example 1.

FIG. 12 is a graph showing the elemental content of the longitudinal cross section of the electrode produced in example 1.

FIG. 13 is an electron micrograph of the surface morphology of the SiCrcarbonitride layer in the electrode prepared in example 2.

FIG. 14 is an electron microscopic view of a cross section of the electrode obtained in example 2.

FIG. 15 is a graph showing the elemental content of the longitudinal cross section of the electrode produced in example 2.

Description of the reference numerals:

The electronic device comprises an electrode-10, a priming layer-11, a transition layer-12, a silicon chromium carbonitride layer-13, an indent-131, a bulge-132, a shell-20, a bulge-21, a display screen-30, an electronic device main body-100, a wearing part-200, a first wearing structure-201, a second wearing structure-202 and an electronic device-300.

Detailed Description

The following are preferred embodiments of the present application, and it should be noted that modifications and variations can be made by those skilled in the art without departing from the principle of the present application, and these modifications and variations are also considered as the protection scope of the present application.

The following disclosure provides many different embodiments, or examples, for implementing different features of the application. In order to simplify the present disclosure, components and arrangements of specific examples are described below. They are, of course, merely examples and are not intended to limit the application. Furthermore, the present application may repeat reference numerals and/or letters in the various examples, which are for the purpose of brevity and clarity, and which do not themselves indicate the relationship between the various embodiments and/or arrangements discussed. In addition, the present application provides examples of various specific processes and materials, but one of ordinary skill in the art will recognize the application of other processes and/or the use of other materials.

The electronic device 300 in the embodiment of the present application may be a device for detecting a physiological parameter of a target object; physiological parameters may be, but are not limited to, heart rate, blood oxygen, sleep, pressure, respiration, exercise, etc. Specifically, the electronic device 300 may acquire signals through the electrode 10, and obtain the required physiological parameters through participation of other electronic components. Of course, the electronic device 300 may also have multiple functions of receiving and sending a phone call, sending and receiving a short message, taking a picture, recording a video, playing music, paying, authenticating, monitoring, calling for help, reminding, positioning, navigating, calibrating, and preventing loss, which are not listed here. Specifically, the electronic device 300 may be, but is not limited to, a mobile phone, a tablet computer, a notebook computer, MP3, MP4, a GPS navigator, a digital camera, a wristwatch (e.g., a smart watch), a bracelet (e.g., a smart bracelet), a foot ring (e.g., a smart foot ring), a ring (e.g., a smart ring), glasses (e.g., smart glasses), etc.

In an embodiment of the present application, the electronic device 300 may be a wearable device, such as a watch, a bracelet, a foot ring, a finger ring, glasses, etc., so as to be more convenient to use. Referring to fig. 1, a schematic structural diagram of an electronic device according to an embodiment of the application is shown; referring to fig. 2, a schematic structural diagram of an electronic device according to another embodiment of the present application is provided, wherein the electronic device 300 includes an electronic device main body 100, and functions of the electronic device 300 are implemented by the electronic device main body 100. The electronic device 300 shown in fig. 1 and 2 is a smart watch and/or a smart bracelet, and the schematic structural diagram of other types of electronic devices 300 is not shown one by one.

In an embodiment of the present application, the electronic device body 100 includes an electrode 10, and signal acquisition is performed through the electrode 10 to achieve detection of a physiological parameter of a target object. It will be appreciated that the number of electrodes 10 on the electronic device body 100 may be one or more, and the specific number may be set according to the detection requirement, and the shape of the electronic device body 100 may be selected according to the requirement. Referring to fig. 3, a schematic structural diagram of an electronic device body according to an embodiment of the application is provided, wherein the electronic device body 100 may include a housing 20, and the electrode 10 may be disposed on a surface of the housing 20. Specifically, in order to achieve contact of the electrode 10 with the target object, the electrode 10 needs to be provided on the outer surface of the housing 20. In one embodiment, the material of the housing 20 includes at least one of glass, plastic, metal and ceramic. The housing 20 made of the above material can not only perform a good bearing function on the electrode 10, but also ensure the strength and the usability of the structure of the electronic device main body 100. Specifically, the material of the housing 20 may be, but is not limited to, glass, stainless steel, titanium alloy, etc. In an embodiment, referring to fig. 3, the housing 20 may have a protrusion 21, and the electrode 10 is disposed on a surface of the protrusion 21, so as to facilitate contact between the electrode 10 and the target object for signal acquisition. Specifically, the cross section of the protrusion 21 may be, but is not limited to, circular, oval, rectangular, rounded rectangular, irregular, or the like.

Referring to fig. 4, which is a schematic cross-sectional view of fig. 3 A-A, the electronic device body 100 may include a display screen 30, where the display screen 30 is connected to the housing 20. The display screen 30 may, but is not limited to, display the obtained physiological parameter value, and the display screen 30 is connected with the housing 20 to form a containing space, so as to accommodate electronic components. Specifically, the display screen 30 may be a touch screen, and the shape of the display screen 30 may be, but is not limited to, circular, oval, quasi-circular, rounded rectangular, etc. Of course, the electronic device 300 may not be provided with the display 30, for example, the housing 20 may have a receiving space for receiving electronic components.

In an embodiment of the present application, the electronic device body 100 may further include a circuit board and a control main board, and the circuit board and the control main board are disposed in the receiving space of the electronic device body 100. It will be appreciated that the receiving space may be formed by the housing 20 or may be formed by the housing 20 and the display screen 30 together. Further, the electrode 10 is connected to the control main board through a circuit board. Specifically, the electronic device 300 may perform ECG (Electrocardiogram) detection on the target object, and when the target object wears the electronic device 300, the electrode 10 of the electronic device 300 may contact with the skin, such as the wrist, the arm, the ankle, the neck, etc., of the target object, and implement the ECG detection through cooperation with other electronic components in the electronic device main body 100, so as to obtain parameters such as the heart rate of the target object; for example, the electrical signals related to the physiological parameters collected by the electrodes 10 are transmitted to the control main board through the circuit board, and the control main board forms an electrocardiogram according to the electrical signals; further, physiological parameters such as an electrocardiogram or heart rate may be displayed through the display screen 30. The above is merely illustrative of one procedure for obtaining a physiological parameter, and it is of course possible to obtain a desired physiological parameter by other procedures, which is not limitative.

In an embodiment of the present application, the electronic device body 100 may further include at least one sensor. The sensor may be configured to sense one or more types of parameters, which may be, but are not limited to, pressure, light, heat, movement, relative motion, and the like. For example, the sensor may include a pressure transducer, a light or optical sensor, a thermal sensor, a position sensor, an accelerometer, a gyroscope, a magnetometer, and the like. By arranging the sensor, the sensor can be matched with signal information acquired by the electrode 10 for use, so that physiological parameters of a target object are enriched; for example, the motion track of the target object, the heart rate variation during the motion and the like can be obtained through the signals acquired by the position sensor and the electrode 10 after processing.

Referring to fig. 1, the electronic device 300 may further have a wearing part 200, and the wearing part 200 is connected to the electronic device main body 100. The wearable device is obtained by providing the wearing part 200 so that the electronic device 300 is worn on a target object, such as a hand, a head, a foot, a neck, or the like of the target object. Specifically, the wearing part 200 may be a mechanical structure or may have adhesiveness, so that the electronic device 300 is worn on the target object; for example, the wearing part 200 may be, but not limited to, a watchband, a wristband, or the like. In an embodiment, the material of the wearing part 200 may include at least one of a metal material, a flexible plastic and a fiber material. Referring to fig. 2, the wearing part 200 may include a first wearing structure 201 and a second wearing structure 202, and the first wearing structure 201 and the second wearing structure 202 are connected with the electronic device main body 100, respectively. Specifically, the ends of the first wearing structure 201 and the second wearing structure 202 may be provided with fasteners to connect the first wearing structure 201 and the second wearing structure 202; for example, when the electronic device 300 is worn, the fasteners may be engaged and the electronic device 300 may be removed by opening the fasteners. The present application does not limit the material, structure, arrangement and shape of the wearing part 200, and only needs to fix the electronic device 300 to the target object more firmly.

In the traditional method, the electrocardio electrode which is most commonly used for electrocardiograph monitoring is an Ag/AgCl electrode with conductive gel, belongs to a wet electrode, has high detection signal to noise ratio, and can be slowly dried due to the fact that the conductive gel has irritation to skin, so that electrocardiograph monitoring is affected. The electronic device 300 provided by the application can realize the detection of the physiological parameters of the target object, the electrodes in the electronic device 300 are biological dry electrodes, the signal acquisition can be carried out without using conductive gel, and meanwhile, the whole structure is more miniaturized and the use is more convenient. Because the dry electrode is not required to be matched with conductive gel, a trace of sweat or environmental water vapor is required to be used as electrolyte when the dry electrode is contacted with the skin, but a gap exists between the electrode and the skin, so that the contact impedance is high, and the signal to noise ratio is low; in the related art, by arranging the needle structure on the surface of the electrode, the needle structure penetrates into the epidermis layer of the skin during detection, so that the contact impedance is reduced, the quality of the acquired signal is improved, but the method still penetrates the skin, the skin infection risk is increased, and the detection comfort is poor.

Therefore, referring to fig. 5, an electrode according to an embodiment of the present application is shown in a schematic cross-sectional view, wherein the electrode 10 includes a base layer 11, a transition layer 12 and a silicon chromium carbonitride layer 13 (CrSiCN) stacked in order, the material of the transition layer 12 includes at least one of silicon chromium nitride (CrSiN) and chromium nitride (CrN), the surface of the silicon chromium carbonitride layer 13 far from the transition layer 12 has a plurality of dimples 131, and the dimples 131 intersect to form a dermatoglyph texture. The surface of the silicon carbide chromium nitride layer 13 far away from the transition layer 12 in the electrode 10 is provided with a dermatoglyph texture, and the surface of the silicon carbide chromium nitride layer 13 provided with the dermatoglyph texture is contacted with skin when the electrode 10 is used; by carrying out bionic design on the surface morphology of the silicon chromium carbonitride layer 13, the contact interface between the electrode 10 and the skin is improved, so that a trace of sweat forms a continuous electrolyte interface between the electrode 10 and the skin, gaps between the electrode 10 and the skin are avoided, the contact impedance between the electrode 10 and the skin is reduced, weak bioelectric signals are collected, meanwhile, the continuous sweat electrolyte interface can improve the quality of detection signals and the accuracy of detection, and the stability and the reliability of the structure of the electrode 10 are ensured by the arrangement of the bottom layer 11 and the transition layer 12; the electrode 10 does not need conductive gel in the use process, avoids the stimulation to the skin, and simultaneously does not stab the skin and damage the skin, thereby being more beneficial to use. In the detection process, the impedance between the electrode 10 and the skin comprises contact impedance, electrode 10 impedance and skin tissue impedance, wherein the electrode 10 impedance and the skin impedance can keep a stable level, and meanwhile, the contact impedance between the electrode 10 and the skin is small, so that the accuracy and consistency of detection are ensured. The electrode 10 provided by the application can be used in the electronic equipment 300, so that the detection performance of the electronic equipment 300 is improved, and the use of the electronic equipment 300 is facilitated.

In the present application, the dermatoglyph texture is texture of skin surface, such as texture growing on skin surface of hands, feet, limbs, etc. Specifically, the skin is animal skin; more specifically, the skin may be human skin, wherein hills, ridges and furrows of the human skin surface form a texture of the human skin surface.

Referring to fig. 6, an enlarged view of the dotted line area in fig. 5 is shown, wherein the surface of the silicon carbide chrome carbonitride layer 13 has a plurality of dimples 131, and the dimples 131 intersect to form a dermatoglyph texture. In the present application, at least some of the plurality of dimples 131 on the surface of the silicon chromium carbonitride layer 13 intersect. In the embodiment of the present application, the depth of the dent 131 is 30nm to 80nm. The uneven appearance of the skin stratum corneum forms the texture of the skin surface, the depth is about 50nm, and the surface appearance of the electrode 10 is subjected to bionic design by arranging the dent 131 with the depth of 30nm-80nm, so that the contact interface between the electrode 10 and the skin is improved, a continuous coupling interface is formed between the electrode 10 and the skin, the continuous distribution of trace sweat in the use process is further improved, the continuous electrolyte interface is ensured to be formed between the electrode 10 and the skin, the contact impedance is further reduced, and the reliability and the accuracy of detection are improved; meanwhile, the dimples 131 with the depth can effectively prevent sweat from invading the transition layer 12 and the primer layer 11, which is beneficial to improving the stability of the overall structure of the electrode 10. Further, the depth of the dent 131 may be 30nm to 45nm, 40nm to 60nm, 50nm to 65nm, 60nm to 70nm, or 65nm to 80nm. Specifically, the depth of the dent 131 may be, but is not limited to, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, or the like.

Referring to fig. 6, in an embodiment of the present application, a protrusion 132 is provided between the plurality of dimples 131. That is, the surface of the silicon chromium carbonitride layer 13 has a plurality of protrusions 132 arranged at intervals, the dimples 131 are arranged between the adjacent protrusions 132, the plurality of dimples 131 intersect to form a net structure, and the protrusions 132 and the dimples 131 are arranged so that the surface of the silicon chromium carbonitride layer 13 presents a dermatoglyph texture.

Referring to fig. 6, L is the lateral dimension of the protrusion 132, W is the width of the dent 131, and H is the depth of the dent 131. Specifically, the lateral dimension is the largest dimension of the surface of the protrusion 132 away from the transition layer 12 in a plane perpendicular to the thickness direction, and the width of the indentation 131 can be regarded as the distance between two adjacent protrusions 132, and the height of the protrusion 132 is the depth of the indentation 131. In an embodiment of the present application, the ratio of the lateral dimension of protrusion 132 to the width of indentation 131 is greater than or equal to 10. That is, the area of the protrusions 132 on the surface of the silicon chromium carbonitride layer 13 far from the transition layer 12 is relatively larger, and the area of the indentations 131 is relatively smaller, so that the surface morphology of the silicon chromium carbonitride layer 13 is closer to the texture on the real skin, and the skin texture bionic design with better effect is realized; meanwhile, when the electrode 10 is in contact with the skin, the interface among the protrusions 132, the indentations 131 and the texture of the skin surface can be better matched so that sweat can be more uniformly and continuously dispersed between the electrode 10 and the skin, the contact resistance is further reduced, and the detection accuracy is improved; specifically, the sweat may be uniformly and continuously distributed between the contact interfaces of the electrode 10 and the skin under the action of capillary force, liquid surface tension, laplace pressure difference, etc., and when the ratio of the transverse dimension of the protrusion 132 to the width of the dent 131 is greater than or equal to 10, the above action is more easily generated, so that the sweat distribution is more uniform and better in continuity, and the contact resistance is further reduced. Further, the ratio of the lateral dimension of protrusion 132 to the width of indentation 131 may be, but is not limited to, 12 or more, 14 or more, 15 or more, 20 or more, etc. In an embodiment of the present application, protrusions 132 have a lateral dimension of 1 μm to 2.5 μm. Further, protrusions 132 have a lateral dimension of 1 μm-1.5 μm, 1.3 μm-1.9 μm, 1.5 μm-2 μm, 1.8 μm-2.3 μm, or 2 μm-2.5 μm. Specifically, the lateral dimensions of protrusions 132 may be, but are not limited to, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, 2 μm, 2.3 μm, 2.5 μm, etc. The size enables the surface appearance of the silicon chromium carbonitride layer 13 to be closer to the texture on the real skin, the skin texture bionic design with better effect is realized, and meanwhile, the micrometer-scale protrusions 132 are easier to generate acting force between the electrode 10 and the skin surface in the skin contact process, so that the continuous distribution of sweat is improved.

In the application, the surface of the silicon carbide chromium nitride layer 13 is provided with the dermatoglyph texture, so that the silicon carbide chromium nitride layer 13 has certain surface roughness, which is beneficial to improving the friction force between the electrode 10 and the skin, thereby reducing the motion artifact generated by the relative sliding of the electrode 10 and the skin in the detection process and improving the detection accuracy. In an embodiment of the application, the roughness of the surface of the silicon chromium carbonitride layer 13 remote from the transition layer 12 is 4.5nm to 12nm. The surface roughness can enable certain friction force to be generated between the electrode 10 and the skin, the influence of motion artifacts is avoided to a certain extent, the detection accuracy and reliability are further improved, meanwhile, the touch feeling of the surface of the silicon carbide chromium nitride layer 13 is still smooth on the macro scale, and the noise influence is reduced as much as possible. Specifically, the roughness of the surface of the silicon chromium carbonitride layer 13 remote from the transition layer 12 may be, but is not limited to, 4.5nm, 5nm, 6nm, 8nm, 9nm, 11nm, 12nm, or the like. Further, the roughness of the surface of the silicon chromium carbonitride layer 13 remote from the transition layer 12 may be 4.5nm to 7nm, 6nm to 9nm, 7.5nm to 10nm, 10nm to 12nm, or the like.

In the embodiment of the present application, the chromium element content of the surface of the silicon carbonitride chromium layer 13 is 22.1at.% to 30.6at.%, the silicon element content is 1.5at.% to 4.8at.%, the carbon element content is 50.6at.% to 61at.%, and the nitrogen element content is 13.3at.% to 16.1at.%. The content of the individual elements in the chromium silicon carbonitride layer 13 is obtained here by means of X-ray photoelectron spectroscopy. In one embodiment, the chromium element content on the surface of the silicon carbide chromium nitride layer 13 is 25at.% to 28.8at.%, the silicon element content is 2.3at.% to 4at.%, the carbon element content is 53.6at.% to 57.7at.%, and the nitrogen element content is 14at.% to 15.8at.%. In the embodiment of the application, the X-ray diffraction pattern of the silicon chromium carbonitride layer 13 has a characteristic diffraction peak with the 2 theta angle of 43-45 degrees. In one embodiment, the silicon chromium carbonitride layer 13 has a (200) diffraction peak of Cr (C, N) in the X-ray diffraction pattern. In one embodiment, silicon element in the silicon chromium carbonitride layer 13 is dissolved between Cr (C, N) grains. Further, silicon element is dissolved in amorphous form of α -Si ₃N₄、α-SiC、α-SiC_xN_y between Cr (C, N) grains.

In the embodiment of the present application, the thickness of the silicon chromium carbonitride layer 13 is 0.6 μm to 1 μm. The silicon carbide chromium nitride layer 13 with the thickness further ensures stable combination in the electrode 10, has certain flexibility, and is beneficial to increasing the bonding degree of the electrode 10 and the skin during detection and improving the detection accuracy. Specifically, the thickness of the silicon chromium carbonitride layer 13 may be, but is not limited to, 0.6 μm, 0.65 μm, 0.7 μm, 0.74 μm, 0.8 μm, 0.88 μm, 0.9 μm, 0.96 μm, 1 μm, or the like. In one embodiment, the thickness of the silicon chromium carbonitride layer 13 may be 0.6 μm to 0.8 μm. In another embodiment, the thickness of the silicon chromium carbonitride layer 13 may be 0.7 μm to 1 μm.

In the present application, the material of the transition layer 12 includes at least one of silicon chromium nitride and chromium nitride. In one embodiment of the present application, the transition layer 12 is a silicon chromium nitride layer. In another embodiment of the present application, the transition layer 12 is a chromium nitride layer. In yet another embodiment of the present application, the transition layer 12 comprises a layer of silicon chromium nitride and a layer of chromium nitride in a stacked arrangement. Further, a silicon chromium nitride layer is provided between the chromium nitride layer and the silicon chromium carbonitride layer 13. By arranging the transition layer 12, the formation of the silicon carbide chromium carbonitride layer 13 is facilitated, the internal stress in the formation process is reduced, and the binding force of the silicon carbide chromium carbonitride layer 13 in the electrode 10 is improved.

In an embodiment of the present application, the thickness of the transition layer 12 is 0.15 μm to 0.35 μm. Thus, the bonding performance of the silicon chromium carbonitride layer 13 in the electrode 10 is further improved, and the stability of the overall structure of the electrode 10 is ensured. Specifically, the thickness of the transition layer 12 may be, but is not limited to, 0.15 μm, 0.2 μm, 0.23 μm, 0.27 μm, 0.3 μm, 0.34 μm, 0.35 μm, or the like. In one embodiment, the thickness of the transition layer 12 may be 0.15 μm to 0.2 μm. In another embodiment, the thickness of the silicon chromium carbonitride layer 13 may be 0.25 μm to 0.35 μm.

In the embodiment of the application, the thickness of the silicon chromium carbonitride layer 13 is greater than the thickness of the transition layer 12; thus, the bonding performance of the silicon chromium carbonitride layer 13 can be ensured, and the resistance of the electrode 10 is not affected excessively. In one embodiment of the present application, the thickness ratio of the silicon chromium carbonitride layer 13 to the transition layer 12 is 2 to 4. The bonding force of the silicon carbide chromium carbonitride layer 13 in the electrode 10 is improved, particularly the bonding force between the transition layer 12 and the silicon carbide chromium carbonitride layer 13 in the edge area of the electrode 10 is improved, and the contact resistance between the electrode 10 and the skin is reduced. Specifically, the thickness ratio of the silicon chromium carbonitride layer 13 and the transition layer 12 may be, but is not limited to, 2, 2.3, 2.5, 2.9, 3, 3.4, 3.5, 3.7, 4, or the like. In one embodiment, the thickness ratio of the silicon chromium carbonitride layer 13 and the transition layer 12 may be 2 to 3. In another embodiment, the thickness ratio of the silicon chromium carbonitride layer 13 and the transition layer 12 may be 3 to 4.

In the present embodiment, the material of the primer layer 11 includes chromium. In one embodiment of the present application, the primer layer 11 is a chromium layer. By providing the primer layer 11, the formation of the transition layer 12 and the silicon chromium carbonitride layer 13 is facilitated, and the bonding performance of the transition layer 12 and the silicon chromium carbonitride layer 13 in the electrode 10 is improved. In the application, the chromium layer can form coarse columnar crystals, the growth of the columnar crystals can be broken by arranging the transition layer 12 to refine grains, the binding force of the silicon carbide chromium nitride layer 13 in the electrode 10 can be improved, and meanwhile, the pores among grain boundaries can be reduced, so that the corrosion resistance under the immersion of liquid (such as sweat) can be improved, the falling-off of a film layer can be avoided, and the stability and the reliability of the electrode 10 can be improved. In the embodiment of the present application, the thickness of the primer layer 11 is 0.1 μm to 0.25 μm; in this way, the adhesion of the transition layer 12 and the silicon chromium carbonitride layer 13 can be ensured without excessively increasing the thickness of the electrode 10. Specifically, the thickness of the primer layer 11 may be, but is not limited to, 0.1 μm, 0.12 μm, 0.15 μm, 0.17 μm, 0.19 μm, 0.2 μm, 0.23 μm, 0.25 μm, or the like. In one embodiment, the thickness of the primer layer 11 may be 0.1 μm to 0.2 μm. In another embodiment, the thickness of the primer layer 11 may be 0.15 μm to 0.25 μm. In one embodiment of the present application, the thickness of the primer layer 11 is less than the thickness of the transition layer 12.

In the embodiment of the present application, the thickness of the electrode 10 is 1 μm to 1.5 μm. The electrode 10 is thin and flexible to facilitate application of the electrode 10 to the skin surface. Specifically, the thickness of the electrode 10 may be, but is not limited to, 1 μm, 1.1 μm, 1.2 μm, 1.24 μm, 1.3 μm, 1.37 μm, 1.4 μm, 1.45 μm, 1.5 μm, or the like. In one embodiment, the thickness of the electrode 10 may be 1 μm to 1.26 μm. In another embodiment, the thickness of the electrode 10 may be 1.35 μm to 1.5 μm.

In an embodiment of the application, the electrode 10 further comprises a substrate, the primer layer 11 being arranged between the substrate and the transition layer 12; the substrate may act as a load bearing substrate for the primer layer 11. In an embodiment of the present application, the material of the substrate may include at least one of glass, plastic, metal and ceramic. Specifically, the material of the substrate may be, but not limited to, glass, stainless steel, titanium alloy, or the like. Of course, the electrode 10 may not be provided with a substrate, the primer layer 11, the transition layer 12 and the silicon chromium carbonitride layer 13 may be directly disposed on the surface of the housing 20, the housing 20 plays a bearing role, and the use of the substrate is omitted. In one embodiment, the primer layer 11 is disposed between the housing 20 and the transition layer 12.

In an embodiment of the present application, the contact resistance of the electrode 10 with the skin is 26400 Ω to 50100Ω at 10 Hz. Under the same conditions, the contact impedance of the Ag-AgCl wet electrode and the skin is 68500 omega, and the electrode 10 provided by the application has lower contact impedance with the skin, thereby being beneficial to the use of the electrode 10. Specifically, the contact resistance of the electrode 10 with the skin at 10Hz may be, but not limited to, 26400 Ω, 28000 Ω, 30000 Ω, 33800 Ω, 37500 Ω, 40000 Ω, 42500 Ω, 46900 Ω, 49300 Ω, 50100 Ω, or the like. In one embodiment, the contact resistance of the electrode 10 to the skin at 10Hz is 26400 Ω -30000 Ω, 30000 Ω -40000 Ω, or 40000 Ω -50100 Ω. The withstand current value is also referred to as bias current tolerance, and means the capability of the electrode 10 to maintain stable dc offset voltage under the long-term action of a minute dc current. In the embodiment of the present application, the withstand current value of the direct current 200nA lower electrode 10 is 0.075V to 0.153V. Further, the current resistance value detection time is more than 8 hours, and the contact area between the electrode 10 to be detected and the skin is 1cm ². In one embodiment, the withstand current value of the DC 200nA lower electrode 10 may be 0.075V-0.100V, 0.100V-0.125V, or 0.125V-0.153V. In the embodiment of the application, an electrode to be detected and two Ag/AgCl wet electrodes can be placed on the surface of skin, the electrode to be detected is placed between the two Ag/AgCl wet electrodes, the distance is 8mm, a working electrode is connected with the electrode to be detected by utilizing an electrochemical workstation, the distribution of a reference electrode and a counter electrode is connected with the two Ag/AgCl wet electrodes, and the detection is carried out by adopting a three-electrode mode; and (3) testing the open circuit voltage for 400s, wherein the contact impedance test frequency is 0.01Hz-300Hz, and detecting the withstand current value by applying 200nA direct current to obtain the contact impedance, the withstand current value and the open circuit voltage of the electrode to be tested. In the application, the contact resistance of the electrode 10 provided by the application and the skin in the detection process is smaller than that of the Ag-AgCl wet electrode and the skin. In one embodiment, the open circuit voltage is 0.096V-0.128V. Specifically, the open circuit voltage may be, but is not limited to, 0.096V, 0.1V, 0.105V, 0.117V, 0.12V, 0.125V, 0.128V, or the like.

The surface of the silicon carbide chromium nitride layer 13 in the electrode 10 provided by the application is provided with the dermatoglyph texture, so that the contact interface between the electrode 10 and the skin is improved, meanwhile, limited sweat forms a continuous electrolyte membrane, and the stability and the reliability of the structure of the electrode 10 are ensured by the primer layer 11 and the transition layer 12, thereby being beneficial to the use of the electrode 10.

The application also provides a preparation method of the electrode 10, which comprises the following steps: the underlayer 11, the transition layer 12 and the silicon chromium carbonitride layer 13 are formed by a deposition method, the underlayer 11, the transition layer 12 and the silicon chromium carbonitride layer 13 are sequentially stacked, the material of the transition layer 12 comprises at least one of silicon chromium nitride and chromium nitride, the surface of the silicon chromium carbonitride layer 13 far away from the transition layer 12 is provided with a plurality of dents 131, and the dents 131 are intersected to form a dermatoglyph texture, so that the electrode 10 is obtained. The preparation method is simple and convenient to operate, can realize the industrial production of the electrode 10, can prepare the electrode 10 in any one of the embodiments, has excellent electrochemical performance of the electrode 10, and is beneficial to the use of the electrode 10.

In the present application, the electrode 10 is prepared by a deposition method. In an embodiment of the application, the depositing comprises at least one of Physical Vapor Deposition (PVD) and Chemical Vapor Deposition (CVD). Physical vapor deposition is a method of performing film deposition by a physical mechanism, and chemical vapor deposition is a method of generating solid deposits by utilizing gaseous or vapor substances to react on a gas phase or gas-solid interface. In an embodiment, physical vapor deposition may include vacuum evaporation, sputtering, ion plating, and the like. Specifically, sputtering may include direct current sputtering, alternating current sputtering, reactive sputtering, magnetron sputtering, and the like, wherein balanced magnetron sputtering and unbalanced magnetron sputtering may be classified according to the difference of the magnetic field configuration distribution of the magnetron cathode. In another embodiment, the chemical vapor deposition process may include a plasma chemical vapor deposition process, a thermal chemical vapor deposition process, a photochemical vapor deposition process, and the like. The electrode 10 prepared by the above-described deposition method has strong internal bonding force and high reliability.

Referring to fig. 7, a flowchart of a method for preparing an electrode according to an embodiment of the application includes:

s101: and depositing a priming layer on the surface of the substrate.

S102: and depositing a transition layer on the surface of the priming layer far away from the substrate, wherein the material of the transition layer comprises at least one of silicon nitride chromium and chromium nitride.

S103: and depositing a silicon carbide chromium carbonitride layer on the surface of the transition layer, wherein the surface of the silicon carbide chromium carbonitride layer far away from the transition layer is provided with a plurality of dents, and the dents are intersected to form dermatoglyph textures, so that the electrode is obtained.

In the present application, a base body is used as a supporting layer, and a primer layer 11, a transition layer 12 and a silicon chromium carbonitride layer 13 are deposited on the surface thereof, thereby obtaining an electrode 10. In particular, the preparation of the primer layer 11, the transition layer 12 and the silicon chromium carbonitride layer 13 may be carried out using the deposition methods mentioned above. In an embodiment of the application, the substrate is further subjected to a cleaning treatment prior to deposition. Specifically, the ultrasonic cleaning can be performed, but not limited to, by ultrasonic cleaning, such as ultrasonic cleaning for 15min-20min, ultrasonic cleaning can be performed in water, and ultrasonic cleaning can be performed in ethanol solution.

In an embodiment of the application, the substrate is further subjected to an argon ion purge prior to deposition. Specifically, the substrate surface is bombarded with argon ions for cleaning and decontamination. In one embodiment of the application, the substrate is bombarded for 5min-20min under conditions of a vacuum of 2.5X10 ^-3Pa-2.7×10^-3 Pa, a substrate bias of-450V to-550V, and an argon ion flux of 15sccm-25 sccm. The argon ion bombardment treatment not only further cleans, but also bombards the surface of the substrate to be rough, thereby being beneficial to increasing the bonding surface between the base layer 11 and the substrate, being beneficial to improving the bonding performance and the wetting performance between the substrate and the base layer 11, and further promoting the stability of the overall structure of the electrode 10. Specifically, the argon ion flux may be, but not limited to, 15sccm, 16sccm, 19sccm, 20sccm, 23sccm, 25sccm, etc., and the bombardment time may be, but not limited to, 5min, 8min, 10min, 12min, 15min, 17min, 20min, etc. In one embodiment, the substrate is bombarded for 5min-10min under a vacuum of 2.5X10 ^-3Pa-2.65×10^- ³ Pa, a negative bias of the substrate of-480V to-520V, and an argon ion flow of 17sccm-22 sccm. In another embodiment, the substrate is bombarded for 10min-20min under a vacuum of 2.6X10 ^-3Pa-2.7×10^-3 Pa, a negative bias of-500V to-550V, and an argon ion flow of 20sccm-25 sccm.

In the application, the substrate can rotate in the deposition process, so that the uniformity of a film layer deposited on the surface of the substrate can be improved. In an embodiment of the present application, the rotational speed of the substrate may be 3rpm/min to 10rpm/min. Specifically, the rotational speed of the substrate may be, but is not limited to, 3rpm/min, 4rpm/min, 5rpm/min, 6pm/min, 7rpm/min, 8rpm/min, 9rpm/min, etc.

In an embodiment of the application, the purity of the target used for deposition is greater than or equal to 99%. Further, the purity of the target material used for deposition is greater than or equal to 99.9%. Still further, the purity of the target material used for deposition is greater than or equal to 99.99%. The target material with the purity can effectively avoid the influence of impurities on the performance of the electrode 10. Specifically, the purity of the chromium target may be, but not limited to, 99%, 99.5%, 99.9%, etc., the purity of the silicon target may be, but not limited to, 99%, 99.9%, 99.99%, etc., and the purity of the graphite target may be, but not limited to, 99%, 99.9%, 99.99%, etc.

In embodiments of the application, the deposition pressure may be in the range of 0.1Pa to 0.5Pa. In particular, the deposition pressure may be, but is not limited to, 0.1Pa, 0.2Pa, 0.3Pa, 0.4Pa, 0.5Pa, etc. Further, the deposition pressure may be 0.1Pa-0.2Pa, 0.2Pa-0.3Pa, 0.3Pa-0.4Pa, or 0.4Pa-0.5Pa, etc. In an embodiment of the present application, the flow rate of the inert gas at the time of deposition is 15sccm to 30sccm. The inert gas is introduced in the deposition process to prevent oxidation, and the inert gas can collide particles generated in the deposition process to influence the deposition of the film, so that the proper deposition rate and the required film morphology of the film are ensured by adopting the inert gas with the flow. Specifically, the flow rate of the inert gas at the time of deposition may be, but not limited to, 15sccm, 17sccm, 20sccm, 23sccm, 25sccm, 28sccm, 30sccm, or the like, and the inert gas may be, but not limited to, argon. In one embodiment, the inert gas flow rate during deposition is 15sccm to 20sccm. In another embodiment, the inert gas flow rate is 20sccm-25sccm during deposition. In yet another embodiment, the inert gas flow rate at the time of deposition is 25sccm-30sccm. In an embodiment of the application, a negative bias is applied to the substrate during deposition. Further, the negative bias voltage is-80V to-60V. Specifically, the negative bias may be, but is not limited to, -80V, -75V, -70V, -68V, or-60V, etc.

In S101, a primer layer 11 is first deposited on the substrate to facilitate bonding of the transition layer 12 and the silicon chromium carbonitride layer 13. In the present embodiment, the underlayer 11 is deposited by magnetron sputtering. Further, the underlayer 11 is deposited by unbalanced magnetron sputtering. In one embodiment of the present application, magnetron sputtering is used to deposit the primer layer 11 using a chromium target as a target. Thus, a chromium-containing primer layer 11, i.e., a chromium layer, can be produced. Further, the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A. In one embodiment, the target power of the chromium target is 40W-70W; that is, a chromium target may be mounted on a radio frequency target site. In another embodiment, the target current of the chromium target is 3A-6A; that is, the chromium target may be mounted on a dc target site. In yet another embodiment, two chromium targets are provided, one of which is mounted on a radio frequency target with a target power of 40W-70W and the other on a DC target with a target current of 3A-6A, thus improving the manufacturing efficiency. Specifically, the target power of the chromium target may be, but is not limited to, 40W, 45W, 50W, 55W, 60W, 65W, 70W, or the like, and the target current of the chromium target may be, but is not limited to, 3A, 4A, 5A, 6A, or the like. In the embodiment of the application, the deposition time of the primer layer 11 can be 8min-12min; thus, the primer layer 11 having a thin thickness and advantageous for improving the bonding force of the transition layer 12 can be obtained. Specifically, the deposition time of the primer layer 11 may be, but is not limited to, 8min, 9min, 10min, 11min, 12min, or the like. Further, the deposition time of the primer layer 11 can be 8min-10min, 10min-11min or11 min-12min, etc. In one embodiment, magnetron sputtering is adopted, a chromium target is used as a target material, inert gas is used as working gas, and deposition is carried out to form a bottom layer 11; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the flow rate of the inert gas is 15sccm-30sccm, and the deposition time is 8min-12min. Further, the underlayer 11 is deposited by unbalanced magnetron sputtering.

In S102, the bonding force of the silicon chromium carbonitride layer 13 is improved by providing the transition layer 12, and the reliability of the overall structure of the electrode 10 is improved. In an embodiment of the present application, the transition layer 12 is deposited using magnetron sputtering. Further, the transition layer 12 is deposited using unbalanced magnetron sputtering. In one embodiment of the present application, magnetron sputtering is used to deposit the transition layer 12 using a chromium target as the target and nitrogen gas. Thus, a chromium nitride-containing transition layer 12, i.e., a chromium nitride layer, can be produced. Further, the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, and the flow rate of nitrogen is 12sccm-18sccm. In one embodiment, the target power of the chromium target is 40W-70W and the flow rate of nitrogen is 12sccm-18sccm; that is, a chromium target may be mounted on a radio frequency target site. In another embodiment, the target current of the chromium target is 3A-6A and the flow rate of nitrogen is 12sccm-18sccm; that is, the chromium target may be mounted on a dc target site. In yet another embodiment, two chromium targets are provided, one of which is mounted on a radio frequency target with a target power of 40W-70W and the other on a DC target with a target current of 3A-6A and a nitrogen flow of 12sccm-18sccm, thus improving the production efficiency. Specifically, the target power of the chromium target may be, but not limited to, 40W, 45W, 50W, 55W, 60W, 65W, 70W, etc., the target current of the chromium target may be, but not limited to, 3A, 4A, 5A, 6A, etc., and the flow rate of nitrogen gas may be, but not limited to, 12sccm, 14sccm, 15sccm, 17sccm, 18sccm, etc. In an embodiment of the present application, the deposition time of the transition layer 12 may be 10min to 20min; thus, the grains can be refined, the pores among grain boundaries can be reduced, and the binding force of the silicon carbide chromium carbonitride layer 13 and the reliability of the electrode 10 can be improved. Specifically, the transition layer 12 may be deposited for a period of time, but is not limited to, 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, etc. Further, the deposition time of the transition layer 12 may be 10min-15min, 12min-16min, 15min-20min, etc. In one embodiment, a magnetron sputtering technology is adopted, a chromium target is used as a target material, and a mixed gas of inert gas and nitrogen is used as a working gas, so that a transition layer 12 is formed by deposition; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the flow rate of inert gas is 20sccm-30sccm, the flow rate of nitrogen is 12sccm-18sccm, and the deposition time is 10min-20min. Further, the transition layer 12 is deposited using unbalanced magnetron sputtering. In another embodiment of the present application, magnetron sputtering is used to deposit the transition layer 12 using a chromium target and a silicon target as targets and nitrogen gas is introduced. Thus, a transitional layer 12 containing silicon chromium nitride, i.e., a silicon chromium nitride layer, can be produced. Further, the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the target power of the silicon target is 600W-800W, and the flow rate of nitrogen is 12sccm-18sccm. In one embodiment, the target power of the chromium target is 40W-70W, the target power of the silicon target is 600W-800W, and the flow rate of nitrogen is 12sccm-18sccm; that is, a chromium target and a silicon target may be mounted on a radio frequency target site. In another embodiment, the target current of the chromium target is 3A-6A, the target power of the silicon target is 600W-800W, and the flow rate of nitrogen is 12sccm-18sccm; that is, the chromium target may be mounted on a dc target and the silicon target on a rf target. In yet another embodiment, two chromium targets are provided, one of which is mounted at the rf target with a target power of 40W-70W and the other of which is mounted at the dc target with a target current of 3A-6A, a silicon target with a target power of 600W-800W and a nitrogen flow of 12sccm-18sccm, thus improving the manufacturing efficiency. Specifically, the target power of the chromium target may be, but is not limited to, 40W, 45W, 50W, 55W, 60W, 65W, 70W, etc., the target current of the chromium target may be, but is not limited to, 3A, 4A, 5A, 6A, etc., the target power of the silicon target may be, but is not limited to, 600W, 680W, 700W, 730W, 770W, 800W, etc., and the flow rate of nitrogen gas may be, but is not limited to, 12sccm, 14sccm, 15sccm, 17sccm, 18sccm, etc. In an embodiment of the present application, the deposition time of the transition layer 12 may be 10min to 20min; thus, the grains can be refined, the pores among grain boundaries can be reduced, and the binding force of the silicon carbide chromium carbonitride layer 13 and the reliability of the electrode 10 can be improved. Specifically, the transition layer 12 may be deposited for a period of time, but is not limited to, 10 minutes, 12 minutes, 15 minutes, 18 minutes, 20 minutes, etc. Further, the deposition time of the transition layer 12 may be 10min-15min, 12min-16min, 15min-20min, etc. In one embodiment, magnetron sputtering is adopted, a chromium target and a silicon target are used as targets, and a mixed gas of inert gas and nitrogen is used as working gas to deposit and form a transition layer 12; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the target power of the silicon target is 600W-800W, the flow rate of inert gas is 15sccm-30sccm, the flow rate of nitrogen is 12sccm-18sccm, and the deposition time is 10min-20min. Further, the transition layer 12 is deposited using unbalanced magnetron sputtering.

In S103, by depositing the silicon chromium carbonitride layer 13 on the surface of the transition layer 12, the bonding force of the silicon chromium carbonitride layer 13 is improved, and simultaneously, the silicon chromium carbonitride layer 13 with the dermatoglyph surface morphology is deposited, so that the contact resistance between the electrode 10 and the skin can be effectively reduced, and the detection accuracy of the electrode 10 is improved.

In the embodiment of the application, the silicon chromium carbonitride layer 13 is deposited by magnetron sputtering. Further, the silicon chromium carbonitride layer 13 is deposited by unbalanced magnetron sputtering. In one embodiment of the present application, magnetron sputtering is used to deposit the silicon chromium carbonitride layer 13 by introducing nitrogen gas with a chromium target, a silicon target and a graphite target as targets. Further, the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the target power of the silicon target is 900W-1100W, the target current of the graphite target is less than or equal to 3A, and the flow rate of nitrogen is 18sccm-25sccm. In one embodiment, the target power of the chromium target is 40W-70W, the target power of the silicon target is 900W-1100W, the target current of the graphite target is less than or equal to 3A, and the flow rate of nitrogen is 18sccm-25sccm; that is, the chromium target and the silicon target may be mounted on a radio frequency target, and the graphite target mounted on a direct current target. In another embodiment, the target current of the chromium target is 3A-6A, the target power of the silicon target is 900W-1100W, the target current of the graphite target is less than or equal to 3A, and the flow rate of nitrogen is 18sccm-25sccm; that is, the chromium target and the graphite target may be mounted on a dc target, and the silicon target on a rf target. In yet another embodiment, two chromium targets are provided, one of which is mounted on a radio frequency target with a target power of 40W-70W and the other of which is mounted on a direct current target with a target current of 3A-6A, a silicon target with a target power of 900W-1100W, a graphite target with a target current of less than or equal to 3A, and a nitrogen flow of 18sccm-25sccm, thus improving the manufacturing efficiency. Specifically, the target power of the chromium target may be, but is not limited to, 40W, 45W, 50W, 55W, 60W, 65W, 70W, etc., the target current of the chromium target may be, but is not limited to, 3A, 4A, 5A, 6A, etc., the target power of the silicon target may be, but is not limited to, 900W, 950W, 1000W, 1050W, 1080W, 1100W, etc., and the flow rate of nitrogen may be, but is not limited to, 18sccm, 19sccm, 20sccm, 22sccm, 25sccm, etc. In one embodiment, the target current of the graphite target is gradually increased from 0 and remains unchanged, and the target current is always less than or equal to 3A. In the application, a graphite target is added in the process of depositing the transition layer 12 to the silicon chromium carbonitride layer 13, so that the silicon chromium carbonitride layer 13 can be prepared by gradually increasing the target current of the graphite target, the internal stress of the silicon chromium carbonitride layer 13 can be further relieved, and the adhesive force can be improved. In the embodiment of the application, the deposition time of the silicon chromium carbonitride layer 13 can be 30min-90min; this ensures bonding with the transition layer 12 while helping to obtain the surface topography of the dermatoglyph texture. Specifically, the deposition time of the silicon chromium carbonitride layer 13 may be, but not limited to, 30min, 40min, 50min, 60min, 70min, 80min, 90min, or the like. Further, the deposition time of the silicon chromium carbonitride layer 13 may be 30min-50min, 50min-70min, 60min-90min, or the like. In an embodiment of the present application, magnetron sputtering is adopted, a chromium target, a silicon target and a graphite target are used as targets, and a mixed gas of inert gas and nitrogen is used as working gas, so as to deposit and form a silicon chromium carbonitride layer 13; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the target power of the silicon target is 900W-1100W, the target current of the graphite target is less than or equal to 3A, the flow rate of inert gas is 15sccm-30sccm, the flow rate of nitrogen is 18sccm-25sccm, and the deposition time is 30min-90min. Further, the silicon chromium carbonitride layer 13 is deposited by unbalanced magnetron sputtering.

It will be appreciated that the present application describes the preparation of the electrode 10 by taking the deposition method of magnetron sputtering as an example, and that other physical vapor deposition or chemical vapor deposition methods may be used to prepare the electrode 10 comprising the underlayer 11, the transition layer 12 and the chromium silicon carbonitride layer 13, which are also within the scope of the present application.

Referring to fig. 8, a flowchart of a method for manufacturing an electronic device main body according to an embodiment of the present application includes:

S201: depositing a priming layer on the surface of the shell.

S202: and depositing a transition layer on the surface of the priming layer far away from the substrate, wherein the material of the transition layer comprises at least one of silicon nitride chromium and chromium nitride.

S203: and depositing a silicon carbide chromium carbonitride layer on the surface of the transition layer, wherein the surface of the silicon carbide chromium carbonitride layer far away from the transition layer is provided with a plurality of dents, and the dents are intersected to form a dermatoglyph texture, so that the electronic equipment main body is obtained.

In the present application, the electronic device main body 100 can be manufactured while the electrode 10 is manufactured using the above manufacturing method; the use of the shell 20 as the bearing layer avoids the use of a substrate, reduces the preparation cost, simultaneously can directly prepare the electronic equipment main body 100, improves the preparation efficiency, directly forms the electrode 10 on the shell 20, is beneficial to improving the binding force between the electrode 10 and the shell 20, and ensures the reliability of the electronic equipment main body 100. The deposition process of the primer layer 11, the transition layer 12 and the silicon chromium carbonitride layer 13 in S201, S202 and S203 may refer to the descriptions in S101, S102 and S103, and the process of the housing 20 may refer to the process of the substrate in S101, which is not described herein. In an embodiment of the present application, the deposition of the primer layer 11 may further include providing a protective layer on the surface of the housing 20. By providing a protective layer on the surface of the case 20, the area where the electrode 10 is not required to be deposited is protected. Specifically, the pre-deposition area is formed by providing a protective layer on the surface of the case 20.

The surface of the silicon chromium carbonitride layer 13 far away from the transition layer 12 in the electrode 10 is provided with the plurality of dents 131, the plurality of dents 131 are intersected to form dermatoglyph textures, a continuous coupling interface can be generated between the electrode 10 and the skin, the contact interface between the electrode 10 and the skin is improved, sweat forms a continuous electrolyte membrane between the electrode 10 and the skin, the contact impedance between the electrode 10 and the skin is further reduced, and the stability and the reliability of the structure of the electrode 10 are ensured by the arrangement of the bottom layer 11 and the transition layer 12; the preparation method of the electrode 10 is simple, convenient to operate and high in preparation yield; the electronic device 300 with the electrode 10 can detect the physiological parameters of the target object, the contact impedance between the electronic device 300 and the skin of the target object is low, and the detection noise is reduced, so that the accuracy of the detection result is ensured, and the use of the electronic device 300 is facilitated.

The effect of the electrode provided by the application is further illustrated by the following specific examples.

Example 1

And preparing an electrode by adopting an unbalanced magnetron sputtering coating system, wherein a glass substrate is ultrasonically cleaned in an ethanol solution for 15min and then placed in the coating system, and a graphite target, a first chromium target, a second chromium target and a silicon target are respectively arranged on a direct current target, a radio frequency target, a direct current target and a radio frequency target, wherein the purity of the chromium target is 99.9%, and the purity of the silicon target and the purity of the graphite target are 99.99%.

After the target material and the glass substrate are clamped, the sealing cover is closed, the vacuum degree of the deposition cavity is pumped to 2.6X10 ^-3 Pa, the substrate is biased to-500V, and argon ions (the flow is 20 sccm) are used for bombarding the surface of the glass substrate for 10min. The working gas pressure of the deposition cavity is 0.12Pa, the argon flow is 20sccm, the rotating speed of the glass matrix is 5rpm/min, the bias voltage of the glass matrix is-60V, the target power and the target current of the chromium target are respectively 50W and 5A, the deposition time is 10min, and a chromium layer is formed on the surface of the glass matrix.

And (3) introducing nitrogen (the flow is 12 sccm), adjusting the target current of the chromium target to 4A, adjusting the power of the silicon target to 600W, keeping other parameters unchanged, depositing for 20min, and forming a silicon nitride chromium layer on the chromium layer.

Finally, the nitrogen flow is adjusted to 25sccm, the power of the silicon target is adjusted to 1000W, the target current of the graphite target is increased from 0 to 3A and kept unchanged, a silicon chromium carbonitride layer with a dermatoglyph texture appearance is formed on the silicon chromium nitride layer for 70min to obtain an electrode, the thickness of the chromium layer in the electrode is 0.167 mu m, the thickness of the silicon chromium nitride layer is 0.276 mu m, the thickness of the silicon chromium carbonitride layer is 0.819 mu m, the depth of dents on the surface of the silicon chromium carbonitride layer is about 50nm, and the surface roughness of the silicon chromium carbonitride layer is 10nm.

Referring to fig. 9, an X-ray diffraction pattern of the silicon chromium carbonitride layer in the electrode prepared in example 1 is shown, wherein the 2 theta angle has a characteristic diffraction peak around 45 deg.. Referring to fig. 10, which is an electron microscope image of the surface morphology of the silicon carbide chromium carbonitride layer in the electrode prepared in example 1, and referring to fig. 11, which is an electron microscope image of the cross section of the electrode prepared in example 1, it can be seen that the surface of the silicon carbide chromium carbonitride layer has a dermatoglyph texture. Meanwhile, an energy spectrometer (EDS) is adopted to carry out element analysis on the longitudinal section of the prepared electrode to obtain an element distribution diagram of the electrode, as shown in fig. 12, silicon element is gradually reduced in the direction from a silicon chromium carbonitride layer to a chromium layer, chromium element is increased and then basically kept unchanged and then reduced, carbon element and nitrogen element are relatively low, the carbon element and the nitrogen element are very close to the longitudinal coordinate in the figure, a deeper line is the nitrogen element, and a shallower line is the carbon element; the carbon content of the silicon chromium carbonitride layer was measured by EDS to be 7.7 at%, 18.4 at%, 8.8 at%, 65.1 at%, 12.1 at%, 38.1 at%, 2.6 at% and 47.1 at%, and the test pattern by EDS resulted in mixing a part of the silicon chromium carbonitride layer during the measurement of the silicon chromium nitride layer, and thus the presence of carbon in the silicon chromium nitride layer was measured.

Example 2

And preparing an electrode by adopting an unbalanced magnetron sputtering coating system, wherein a glass substrate is ultrasonically cleaned in an ethanol solution for 20min and then is placed in the coating system, and a graphite target, a first chromium target, a second chromium target and a silicon target are respectively arranged on a direct current target, a radio frequency target, a direct current target and a radio frequency target, wherein the purity of the chromium target is 99.9%, and the purity of the silicon target and the purity of the graphite target are 99.99%.

After the target material and the glass substrate are clamped, the sealing cover is closed, the vacuum degree of the deposition cavity is pumped to 2.7X10 ^-3 Pa, the substrate is biased to-500V, and argon ions (the flow is 20 sccm) are used for bombarding the surface of the glass substrate for 15min. The working gas pressure of the deposition cavity is 0.12Pa, the argon flow is 20sccm, the rotating speed of the glass matrix is 5rpm/min, the bias voltage of the glass matrix is-60V, the target power and the target current of the chromium target are respectively 50W and 5A, the deposition time is 8min, and a chromium layer is formed on the surface of the glass matrix.

And (3) introducing nitrogen (the flow is 18 sccm), enabling the power of the silicon target to be 800W, keeping other parameters unchanged, and depositing for 15min to form a silicon nitride chromium layer on the chromium layer.

Finally, the target current of the chromium target is adjusted to 4A, the target power of the silicon target is adjusted to 1000W, the target current of the graphite target is increased from 0 to 3A and kept unchanged, a silicon chromium carbonitride layer with a dermatoglyph texture appearance is formed on the silicon chromium nitride layer for 60min to obtain an electrode, the thickness of the chromium layer in the electrode is 0.136 mu m, the thickness of the silicon chromium nitride layer is 0.179 mu m, the thickness of the silicon chromium carbonitride layer is 0.617 mu m, the depth of a dent on the surface of the silicon chromium carbonitride layer is about 38nm, and the surface roughness of the silicon chromium carbonitride layer is 7nm.

Referring to fig. 13, which is an electron micrograph of the surface morphology of the silicon carbide chromium carbonitride layer in the electrode prepared in example 2, and referring to fig. 14, which is an electron micrograph of the cross section of the electrode prepared in example 2, it can be seen that the surface of the silicon carbide chromium carbonitride layer has a dermatoglyph texture. Meanwhile, elemental analysis was performed on the longitudinal section of the obtained electrode by using an energy spectrometer (EDS), and an elemental distribution diagram of the electrode was obtained, and as shown in fig. 15, it was found that the silicon element gradually decreased in the direction from the silicon chromium carbonitride layer to the chromium layer, the chromium element increased and then remained substantially unchanged and then decreased, and the carbon element and the nitrogen element were relatively low, in the figure, very close to the ordinate, the silicon chromium nitride layer was examined by EDS for 22.5at.% of the carbon element, 13.6at.% of the nitrogen element, 23.3at.% of the silicon element, 40.6at.% of the chromium element, 20.6at.% of the carbon element, 32.1at.% of the silicon element, 7.9at.% of the silicon element, and 39.5at.% of the chromium element.

Example 3

The difference from example 2 is that the silicon target was kept closed after the preparation of the chromium layer to prepare a chromium nitride layer, and an electrode comprising the chromium layer, the chromium nitride layer and the silicon chromium carbonitride layer was laminated was prepared.

Example 4

An electrode comprising a laminated arrangement substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the surface of the silicon chromium carbonitride layer far away from the silicon chromium nitride layer is provided with dents and protrusions, the dents and the protrusions form dermatoglyph textures, the depth of the dents is 60nm, the transverse dimension of the protrusions is 1.2 mu m, and the surface roughness of the silicon chromium carbonitride layer is 9nm.

Example 5

An electrode comprising a laminated arrangement substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the surface of the silicon chromium carbonitride layer far away from the silicon chromium nitride layer is provided with a dermatoglyph texture, the surface roughness of the silicon chromium carbonitride layer is 4.5nm, the thickness of the chromium layer is 0.12 mu m, the thickness of the transition layer is 0.2 mu m, and the thickness of the silicon chromium carbonitride layer is 0.6 mu m.

Example 6

An electrode comprising a laminated arrangement substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the surface of the silicon chromium carbonitride layer far away from the silicon chromium nitride layer is provided with a dermatoglyph texture, the surface roughness of the silicon chromium carbonitride layer is 11nm, the thickness of the chromium layer is 0.2 mu m, the thickness of the transition layer is 0.35 mu m, and the thickness of the silicon chromium carbonitride layer is 1 mu m.

Example 7

An electrode comprising a laminated arrangement substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the surface of the silicon chromium carbonitride layer far away from the silicon chromium nitride layer is provided with a dermatoglyph texture, the surface roughness of the silicon chromium carbonitride layer is 20nm, the thickness of the chromium layer is 0.12 mu m, the thickness of the transition layer is 0.2 mu m, and the thickness of the silicon chromium carbonitride layer is 0.6 mu m.

Example 8

An electrode comprising a laminated arrangement substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the surface of the silicon chromium carbonitride layer far away from the silicon chromium nitride layer is provided with a dermatoglyph texture, the surface roughness of the silicon chromium carbonitride layer is 11nm, the thickness of the chromium layer is 0.2 mu m, the thickness of the transition layer is 0.35 mu m, and the thickness of the silicon chromium carbonitride layer is 0.6 mu m.

Example 9

An electrode comprising a laminated arrangement substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the surface of the silicon chromium carbonitride layer far away from the silicon chromium nitride layer is provided with a dermatoglyph texture, the surface roughness of the silicon chromium carbonitride layer is 11nm, the thickness of the chromium layer is 0.2 mu m, the thickness of the transition layer is 0.2 mu m, and the thickness of the silicon chromium carbonitride layer is 1 mu m.

Comparative example 1

An electrode comprising a laminate of a substrate, a chromium layer, a silicon chromium nitride layer and a silicon chromium carbonitride layer, wherein the thickness of the chromium layer is 0.167 mu m, the thickness of the silicon chromium nitride layer is 0.276 mu m, the thickness of the silicon chromium carbonitride layer is 0.819 mu m, and the surface of the silicon chromium carbonitride layer has no skin texture.

Comparative example 2

An electrode comprises a substrate and a silicon chromium carbonitride layer arranged on the surface of the substrate.

Comparative example 3

An electrode includes a laminate arrangement substrate, a chromium layer, and a silicon chromium carbonitride layer.

Comparative example 4

An electrode includes a laminate arrangement substrate, a silicon chromium nitride layer, and a silicon chromium carbonitride layer.

The electrodes prepared in examples 1 to 9 and comparative example 1 and the Ag/AgCl wet electrode were used as electrodes to be tested, and the following experiments were performed, respectively, while the film layer on the surface of the substrate in the electrodes prepared in comparative examples 2 to 3 was easily peeled off, and the use requirements could not be satisfied, and the following experiments were not performed. Placing an electrode to be detected and two Ag/AgCl wet electrodes on the surface of skin, wherein the electrode to be detected is placed between the two Ag/AgCl wet electrodes, the distance is 8mm, a working electrode is connected with the electrode to be detected by using an electrochemical workstation, a reference electrode and a counter electrode are distributed and connected with the two Ag/AgCl wet electrodes, and detection is performed by adopting a three-electrode mode; and (3) testing the open circuit voltage for 400s, wherein the contact impedance test frequency is 0.01Hz-300Hz, and detecting the withstand current value by applying 200nA direct current to obtain the contact impedance, the withstand current value and the open circuit voltage of the electrode to be tested. The contact resistance between the electrode prepared in examples 1-9 and the skin is between 27000 omega and 49500 Ω, which is smaller than the contact resistance between the electrode prepared in comparative examples and the Ag/AgCl wet electrode and the skin (68500 omega), which shows that the electrode provided by the application can effectively improve the interface performance with the skin, and the contact resistance between the electrode prepared in examples 1-9 and the skin is better than the contact resistance between the electrode prepared in example 5 and the skin, which is better than the contact resistance between the electrode prepared in example 7, and the contact resistance between the electrode prepared in example 6 and the skin is better than the electrode prepared in examples 8-9, and the open circuit voltage of the electrode prepared in examples 1-9 in the test is between 0.096V and 0.128V, and the resistance value is between 0.075V and 0.153V, which shows that the electrode has good stability and is beneficial to use.

The foregoing has outlined rather broadly the more detailed description of embodiments of the application in order that the principles and embodiments of the application may be better understood, and in order that the present application may be better understood; meanwhile, as those skilled in the art will have variations in the specific embodiments and application scope in accordance with the ideas of the present application, the present description should not be construed as limiting the present application in view of the above.

Claims

1. An electrode, characterized by, including the priming layer, transition layer and the silicon chromium carbonitride layer that stack up in proper order and set up, the material of transition layer includes at least one of silicon chromium nitride and chromium nitride, the silicon chromium carbonitride layer keeps away from the surface of transition layer has a plurality of dents, a plurality of the dent intersects and forms skin line texture, the electrode satisfies at least one of following condition:

(1) The roughness of the surface of the silicon chromium carbonitride layer far away from the transition layer is 4.5nm-12nm;

(2) The contact resistance of the electrode with the skin is 26400 Ω -50100Ω under the condition of 10 Hz.

2. The electrode of claim 1, wherein the indentations have a depth of 30nm to 80nm.

3. The electrode of claim 1, wherein a plurality of the dimples have protrusions therebetween, the ratio of the lateral dimension of the protrusions to the width of the dimples being greater than or equal to 10.

4. An electrode according to claim 3, wherein the protrusions have a lateral dimension of 1 μm to 2.5 μm.

5. The electrode of claim 1, wherein the thickness ratio of the silicon chromium carbonitride layer and the transition layer is 2 to 4.

6. The electrode of claim 1, wherein the primer layer has a thickness of 0.1 μm to 0.25 μm;

the thickness of the transition layer is 0.15-0.35 mu m;

the thickness of the silicon chromium carbonitride layer is 0.6 mu m-1 mu m.

7. The electrode of claim 1, wherein the electrode has a thickness of 1 μm to 1.5 μm.

8. The electrode of claim 1, wherein the primer layer comprises chromium.

9. The electrode of claim 1, wherein the electrode has a resistance value of 0.075V to 0.153V at 200nA dc and an open circuit voltage of 0.096V to 0.128V.

10. A method of making an electrode comprising:

Forming a priming layer, a transition layer and a silicon chromium carbonitride layer by a deposition method, wherein the priming layer, the transition layer and the silicon chromium carbonitride layer are sequentially laminated, the material of the transition layer comprises at least one of silicon chromium nitride and chromium nitride, the surface of the silicon chromium carbonitride layer far away from the transition layer is provided with a plurality of dents, the dents are intersected to form a dermatoglyph texture, and the electrode is obtained and meets at least one of the following conditions:

11. The method of manufacturing of claim 10, wherein forming the silicon chromium carbonitride layer by a deposition method comprises:

The magnetron sputtering is adopted, a chromium target, a silicon target and a graphite target are used as targets, and a mixed gas of inert gas and nitrogen is used as working gas, so that the silicon carbide chromium nitride layer is formed by deposition; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the target power of the silicon target is 900W-1100W, the target current of the graphite target is less than or equal to 3A, the flow rate of the inert gas is 15sccm-30sccm, the flow rate of the nitrogen gas is 18sccm-25sccm, and the deposition time is 30min-90min.

12. The method of manufacturing of claim 10, wherein forming the transition layer by a deposition method comprises:

The transition layer is formed by adopting magnetron sputtering, taking a chromium target and a silicon target as targets and taking mixed gas of inert gas and nitrogen as working gas through deposition; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the target power of the silicon target is 600W-800W, the flow rate of the inert gas is 15sccm-30sccm, the flow rate of the nitrogen gas is 12sccm-18sccm, and the deposition time is 10min-20min; or (b)

The magnetron sputtering technology is adopted, a chromium target is used as a target material, and a mixed gas of inert gas and nitrogen is used as working gas, so that the transition layer is formed by deposition; the target power of the chromium target is 40W-70W and/or the target current of the chromium target is 3A-6A, the flow rate of the inert gas is 20sccm-30sccm, the flow rate of the nitrogen gas is 12sccm-18sccm, and the deposition time is 10min-20min.

13. The electronic equipment is characterized by comprising an electronic equipment main body, wherein the electronic equipment main body comprises an electrode, the electrode comprises a bottoming layer, a transition layer and a silicon chromium carbonitride layer which are sequentially stacked, the material of the transition layer comprises at least one of silicon chromium nitride and chromium nitride, the surface of the silicon chromium carbonitride layer, which is far away from the transition layer, is provided with a plurality of dents, the dents are intersected to form a dermatoglyph texture, and the electrode meets at least one of the following conditions: