Electrodes, their preparation methods, and electronic devices

Abstract

This application provides an electrode comprising a bottom layer, a tungsten carbide layer, and a tungsten-doped diamond-like carbon layer stacked sequentially. The electrode provided by this application exhibits low impedance, excellent wear resistance, and excellent corrosion resistance, thereby improving detection accuracy and extending service life, which is beneficial for its use in electronic devices. This application also provides a method for preparing the electrode and an electronic device thereof.

Description

Technical Field

[0001] This application belongs to the field of electronic product technology, specifically relating to electrodes and their preparation methods, and electronic devices. Background Technology

[0002] With the continuous development of technology, smartwatches, smart bracelets, and other electronic devices are emerging in large numbers, and more and more of these devices have the function of detecting various physiological parameters such as heart rate, blood oxygen, sleep, and stress. However, in the current detection process, the impedance between the electronic device and the user's skin is relatively high, resulting in high noise in the detection signal and thus affecting the accuracy of the detection results. Summary of the Invention

[0003] In view of this, this application provides an electrode, a method for preparing the same, and an electronic device thereof.

[0004] In one aspect, this application provides an electrode comprising a base layer, a tungsten carbide layer, and a tungsten-doped diamond-like layer stacked sequentially.

[0005] Secondly, this application provides a method for preparing an electrode, comprising forming an underlayer, a tungsten carbide layer and a tungsten-doped diamond-like layer by deposition, wherein the underlayer, the tungsten carbide layer and the tungsten-doped diamond-like layer are stacked sequentially to obtain an electrode.

[0006] Thirdly, this application provides an electronic device, including an electronic device body, the electronic device body including an electrode, the electrode including a base layer, a tungsten carbide layer and a tungsten-doped diamond-like layer stacked sequentially.

[0007] The electrode provided in this application exhibits low contact impedance with the skin and excellent corrosion resistance. Furthermore, the tungsten-doped diamond-like layer surface is wear-resistant, enhancing the electrode's wear resistance. The underlayer, tungsten carbide layer, and tungsten doping ensure the stability and reliability of the electrode structure. The electrode is simple to prepare, easy to operate, and has a high yield rate. Electronic devices equipped with this electrode can detect the physiological parameters of the target object. The low contact impedance between the electronic device and the target object's skin reduces detection noise, thus ensuring the accuracy of the detection results. Simultaneously, its excellent corrosion and wear resistance improves its service life and enhances the product competitiveness of the electronic device. Attached Figure Description

[0008] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the embodiments of this application will be described below.

[0009] Figure 1 A schematic diagram of the structure of an electronic device provided in one embodiment of this application.

[0010] Figure 2A schematic diagram of the structure of an electronic device provided in another embodiment of this application.

[0011] Figure 3 This is a schematic diagram of the structure of the main body of an electronic device provided in one embodiment of this application.

[0012] Figure 4 for Figure 3 A schematic diagram of the cross section of AA.

[0013] Figure 5 This is a cross-sectional schematic diagram of an electrode provided in one embodiment of this application.

[0014] Figure 6 A cross-sectional schematic diagram of an electrode provided for another embodiment of this application.

[0015] Figure 7 This is a flowchart illustrating a method for preparing an electrode according to an embodiment of this application.

[0016] Figure 8 A flowchart illustrating the method for preparing the main body of an electronic device according to an embodiment of this application.

[0017] Figure 9 The image shows an electron microscope (EM) image of the surface morphology of the tungsten-doped diamond-like layer in the electrode prepared in Example 1.

[0018] Figure 10 This is an electron microscope image of the cross-section of the electrode obtained in Example 1.

[0019] Figure 11 The image shows an electron microscope (EM) image of the surface morphology of the tungsten-doped diamond-like layer in the electrode prepared in Example 2.

[0020] Figure 12 This is an electron microscope image of the cross-section of the electrode obtained in Example 2.

[0021] Figure 13 X-ray diffraction patterns of the electrodes prepared in Examples 1 and 2.

[0022] Figure 14 The graph shows the results of friction coefficient testing on the electrode surfaces prepared in Examples 1 and 2.

[0023] Figure 15 The images show the results of wear mark detection on the electrode surfaces obtained in Examples 1 and 2.

[0024] Figure 16 The image shows the Raman spectrum of the tungsten-doped diamond-like layer surface of the electrode prepared in Example 1.

[0025] Figure 17 The image shows the Raman spectrum of the tungsten-doped diamond-like layer surface of the electrode prepared in Example 2.

[0026] Figure 18 The image shows the AC impedance spectrum of the electrode prepared in Example 1.

[0027] Figure 19 The image shows the AC impedance spectrum of the electrode prepared in Example 2.

[0028] Label Explanation:

[0029] Electrode-10, Underlayer-11, Tungsten carbide layer-12, Tungsten-doped diamond-like layer-13, Substrate-14, Housing-20, Protrusion-21, Display screen-30, Electronic device body-100, Wearable part-200, First wearable structure-201, Second wearable structure-202, Electronic device-300. Detailed Implementation

[0030] The following are preferred embodiments of this application. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principles of this application, and these improvements and modifications are also considered to be within the scope of protection of this application.

[0031] The following disclosure provides many different embodiments or examples for implementing different structures of this application. To simplify the disclosure, specific examples of components and arrangements are described below. Of course, these are merely examples and are not intended to limit the scope of this application. Furthermore, reference numerals and / or letters may be repeated in different examples; such repetition is for simplification and clarity and does not in itself indicate a relationship between the various embodiments and / or arrangements discussed. In addition, various specific examples of processes and materials are provided in this application, but those skilled in the art will recognize the application of other processes and / or the use of other materials.

[0032] The electronic device 300 in this application embodiment can be a device for detecting physiological parameters of a target object; physiological parameters may include, but are not limited to, heart rate, blood oxygen, sleep, pressure, respiration, and exercise. Specifically, the electronic device 300 can acquire signals through electrodes 10, and then obtain the required physiological parameters through the participation of other electronic components. Of course, the electronic device 300 may also have various functions such as making and receiving calls, sending and receiving text messages, taking photos, recording videos, playing music, making payments, identity verification, monitoring, emergency calls, reminders, positioning, navigation, calibration, and intelligent anti-loss, which are not listed here. Specifically, the electronic device 300 may include, but is not limited to, mobile phones, tablets, laptops, MP3 players, MP4 players, GPS navigators, digital cameras, watches (such as smartwatches), bracelets (such as smart bracelets), anklets (such as smart ankle bracelets), rings (such as smart rings), and glasses (such as smart glasses).

[0033] In one embodiment of this application, the electronic device 300 can be a wearable device, such as a watch, bracelet, anklet, ring, or glasses, thereby making it more convenient to use. Please refer to [link to relevant documentation]. Figure 1 This is a schematic diagram of the structure of an electronic device provided in one embodiment of this application; please refer to [link / reference]. Figure 2 This is a schematic diagram of the structure of an electronic device provided in another embodiment of this application, wherein the electronic device 300 includes an electronic device body 100, and the functions of the electronic device 300 are realized through the electronic device body 100. Figure 1 and Figure 2 The electronic device 300 shown is a smartwatch and / or smart bracelet. Structural diagrams of other types of electronic devices 300 are not shown one by one.

[0034] In this embodiment, the electronic device body 100 includes electrodes 10 for signal acquisition to detect physiological parameters of the target object. It is understood that the number of electrodes 10 on the electronic device body 100 can be one or more, the specific number being set according to detection needs, and the shape of the electronic device body 100 being selected as needed. Please refer to [link to relevant documentation]. Figure 3 This is a schematic diagram of the structure of an electronic device body according to an embodiment of this application. The electronic device body 100 may include a housing 20, and electrodes 10 may be disposed on the surface of the housing 20. Specifically, in order to achieve contact between the electrodes 10 and the target object, the electrodes 10 need to be disposed 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 materials can not only provide good support for the electrodes 10, but also ensure the structural strength and performance of the electronic device body 100. Specifically, the material of the housing 20 may be, but is not limited to, stainless steel, titanium alloy, etc. In one embodiment, please refer to... Figure 3 The housing 20 may have a protrusion 21, and the electrode 10 is disposed on the surface of the protrusion 21, which is more conducive to the 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, a circle, an ellipse, a rectangle, a rounded rectangle, or an irregular shape.

[0035] Please see Figure 4 ,for Figure 3The cross-sectional diagram of AA shows that the main body 100 of the electronic device may include a display screen 30, which is connected to the housing 20. The display screen 30 may display, but is not limited to, the obtained physiological parameter values. The connection between the display screen 30 and the housing 20 forms a receiving space for accommodating electronic components. Specifically, the display screen 30 may be a touch screen, and its shape may be, but is not limited to, circular, elliptical, near-circular, or rounded rectangle. Alternatively, the electronic device 300 may not have a display screen 30; for example, the housing 20 may have a receiving space for accommodating electronic components.

[0036] In one embodiment of this application, the electronic device body 100 may further include a circuit board and a control motherboard, which are disposed within the accommodating space of the electronic device body 100. It is understood that this accommodating space may be formed by the housing 20, or it may be formed jointly by the housing 20 and the display screen 30. Further, the electrodes 10 are connected to the control motherboard via the circuit board. Specifically, the electronic device 300 can perform ECG (Electrocardiogram) detection on a target object. When the target object wears the electronic device 300, the electrodes 10 of the electronic device 300 can contact the target object's skin, such as the wrist, arm, ankle, or neck, and achieve ECG detection through cooperation with other electronic components in the electronic device body 100, obtaining parameters such as the target object's heart rate. For example, the electrical signals related to the physiological parameters collected by the electrodes 10 are transmitted to the control motherboard via the circuit board, and the control motherboard generates an ECG based on these electrical signals. Further, the ECG or physiological parameters such as heart rate can be displayed on the display screen 30. The above only exemplifies one process for obtaining physiological parameters; of course, other processes can also be used to obtain the required physiological parameters, and this is not limited to this.

[0037] In one embodiment of this application, the electronic device body 100 may further include at least one sensor. The sensor can be configured to sense one or more types of parameters, including but not limited to pressure, light, heat, movement, relative motion, etc. 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, etc. By setting up the sensor, it can be used in conjunction with the signal information collected by the electrode 10 to enrich the physiological parameters of the target object; for example, the motion trajectory of the target object and the heart rate changes during movement can be obtained after processing by the signals collected by the position sensor and the electrode 10.

[0038] Please see Figure 1The electronic device 300 may also have a wearable part 200, which is connected to the main body 100 of the electronic device. By providing the wearable part 200, the electronic device 300 is worn on a target object, such as the target object's hand, head, feet, neck, etc., thereby obtaining a wearable device. Specifically, the wearable part 200 can be a mechanical structural component or can be adhesive, thereby allowing the electronic device 300 to be worn on the target object; for example, the wearable part 200 can be, but is not limited to, a watch strap or wristband. In one embodiment, the material of the wearable part 200 may include at least one of metal, flexible plastic, and fiber materials. Please refer to [link to relevant documentation]. Figure 2 The wearable part 200 may include a first wearable structure 201 and a second wearable structure 202, which are respectively connected to the main body 100 of the electronic device. Specifically, the ends of the first wearable structure 201 and the second wearable structure 202 may be provided with fastening members to connect the first wearable structure 201 and the second wearable structure 202; for example, the fastening members are engaged when the electronic device 300 is worn, and the electronic device 300 can be removed by opening the fastening members. This application does not limit the material, structure, setting method, or shape of the wearable part 200, as long as it can securely fix the electronic device 300 to the target object.

[0039] In traditional methods, the most commonly used electrocardiogram (ECG) electrodes for monitoring are Ag / AgCl electrodes with conductive gel. These are wet electrodes, offering a high signal-to-noise ratio. However, the conductive gel is irritating to the skin and dries out gradually, affecting ECG monitoring. The electronic device 300 provided in this application can detect the physiological parameters of a target object. The electrodes in the electronic device 300 are biological dry electrodes, eliminating the need for conductive gel and enabling signal acquisition. Furthermore, the overall structure is more compact and easier to use. Since dry electrodes do not require conductive gel, they rely on trace amounts of sweat or ambient moisture as electrolytes when in contact with the skin. However, the contact impedance between the electrode and skin is high, resulting in a low signal-to-noise ratio. Moreover, the direct contact between the dry electrode and the skin means that sweat on the skin surface can corrode the dry electrode and generate electrochemical noise that interferes with signal acquisition. For example, stainless steel dry electrodes can corrode after prolonged contact with sweat, generating electrochemical noise.

[0040] Therefore, this application provides an electrode 10, please refer to... Figure 5 This is a cross-sectional schematic diagram of an electrode provided in one embodiment of this application. The electrode 10 includes a base layer 11, a tungsten carbide layer 12, and a tungsten-doped diamond-like carbon layer 13, which are stacked sequentially. When in use, the tungsten-doped diamond-like carbon layer 13 of the electrode 10 provided in this application comes into contact with the skin. Tungsten is doped into the diamond layer to generate a tungsten carbide microcrystalline phase, thereby reducing the number of carbon coordination atoms in the amorphous carbon-based network, resulting in a decrease in the number of sp atoms in the amorphous carbon network. 2The increased hybrid bond content improves the conductivity of the film, thereby reducing contact resistance. Electrode 10 exhibits excellent corrosion resistance, avoiding corrosion noise and improving detection accuracy. The combination of the underlayer 11, tungsten carbide layer 12, and tungsten doping ensures the stability and reliability of the electrode 10 structure. In particular, tungsten doping in the diamond-like carbon reduces the internal stress of the tungsten-doped diamond-like carbon layer 13 and improves the bonding force with the tungsten carbide layer 12. Furthermore, this electrode 10 does not require conductive gel during use, avoiding skin irritation. The film composed of the underlayer 11, tungsten carbide layer 12, and tungsten-doped diamond-like carbon layer 13 exhibits high conductivity, low contact resistance, and excellent corrosion and wear resistance. This application provides the application of this film in electrode 10, thereby improving the performance of electrode 10 and facilitating its use, especially meeting the requirements for ECG signal processing. The electrode 10 provided in this application can be used in the aforementioned electronic device 300, improving the detection performance of the electronic device 300 and benefiting its use.

[0041] Please see Figure 6 This is a cross-sectional schematic diagram of an electrode provided in another embodiment of this application. The electrode 10 may further include a substrate 14, with a base layer 11 disposed between the substrate 14 and the tungsten carbide layer 12. The substrate 14 can support the base layer 11, the tungsten carbide layer 12, and the tungsten-doped diamond-like carbon (TDLC) layer 13. In this embodiment, the material of the substrate 14 may include at least one of glass, plastic, metal, and ceramic. Specifically, the material of the substrate 14 may be, but is not limited to, stainless steel, titanium alloy, etc. In one embodiment of this application, the material of the substrate 14 includes metal. Metal is easily oxidized and corroded. By setting the base layer 11, the tungsten carbide layer 12, and the tungsten-doped diamond-like carbon (TDLC) layer 13, the substrate 14 can be protected, avoiding the influence of corrosion noise and improving the service life and detection accuracy of the electrode 10. At this time, the base layer 11 plays a transition and buffer role, avoiding the problem of excessive internal stress and easy detachment caused by directly setting the tungsten carbide layer 12 and the tungsten-doped diamond-like carbon (TDLC) layer 13 on the substrate 14, thus improving the overall structural stability of the electrode 10. Of course, the electrode 10 may not have a substrate 14. The underlayer 11, tungsten carbide layer 12, and tungsten-doped diamond-like carbon layer 13 can be directly disposed on the surface of the housing 20, with the housing 20 serving as a load-bearing structure, thus eliminating the need for a substrate 14. In one embodiment, the underlayer 11 is disposed between the housing 20 and the tungsten carbide layer 12.

[0042] In this application embodiment, the material of the underlayer 11 includes chromium. In one embodiment of this application, the underlayer 11 is a chromium layer. By setting the aforementioned underlayer 11, it is beneficial to the formation of the tungsten carbide layer 12 and the tungsten-doped diamond-like carbon (TDLC) layer 13, thereby improving the bonding performance of the tungsten carbide layer 12 and the TDLC layer 13 in the electrode 10. In this application, the chromium layer can form coarse columnar crystals. By setting the tungsten carbide layer 12, the growth of the columnar crystals can be interrupted, thus refining the grains and improving the bonding force of the TDLC layer 13 in the electrode 10. In this application embodiment, the thickness of the underlayer 11 is 0.1 μm-2 μm; thus, the adhesion of the tungsten carbide layer 12 and the TDLC layer 13 can be guaranteed without excessively increasing the thickness of the electrode 10. Specifically, the thickness of the underlayer 11 can be, but is not limited to, 0.1 μm, 0.5 μm, 0.6 μm, 0.8 μm, 0.9 μm, 1 μm, 1.5 μm, or 1.8 μm. In one embodiment, the thickness of the underlayer 11 can be 0.1 μm-1 μm. In another embodiment, the thickness of the underlayer 11 can be 0.1 μm-0.5 μm. In one embodiment of this application, the thickness of the underlayer 11 is less than the thickness of the tungsten carbide layer 12.

[0043] In this application, the tungsten carbide layer 12 serves as a transition layer, improving the adhesion of the tungsten-doped diamond-like carbon (TDLC) layer 13 to the electrode 10. Simultaneously, the presence of the tungsten carbide layer 12 also helps reduce the impedance of the electrode 10. In this embodiment, the thickness of the tungsten carbide layer 12 is 0.1 μm-2 μm. This further improves the bonding performance of the tungsten-doped diamond-like carbon (TDLC) layer 13 in the electrode 10, ensuring the overall structural stability of the electrode 10, and simultaneously reducing the impedance of the electrode 10. Specifically, the thickness of the tungsten carbide layer 12 can be, but is not limited to, 0.1 μm, 0.2 μm, 0.5 μm, 0.8 μm, 1 μm, 1.5 μm, 1.7 μm, or 2 μm. In one embodiment, the thickness of the tungsten carbide layer 12 can be 0.1 μm-1 μm. In another embodiment, the thickness of the tungsten-doped diamond-like carbon (TDLC) layer 13 can be 1 μm-2 μm.

[0044] In this application, the tungsten-doped diamond-like carbon layer 13 avoids the problems of high internal stress and poor bonding strength in diamond-like carbon layers. Simultaneously, the tungsten doping reduces the number of carbon coordinating atoms. This reduction in the number of coordinating atoms and the decrease in local carbon density leads to sp... 2The increased hybrid bond content enhances the conductivity of the tungsten-doped diamond-like carbon (TDLC) layer 13, reducing the contact resistance of the electrode 10; furthermore, the tungsten doping improves wear resistance. In this embodiment, the tungsten content in the TDLC layer 13 gradually decreases along the direction from the tungsten carbide layer 12 to the TDLC layer 13. This gradual change in tungsten content in the TDLC layer 13 helps to further alleviate internal stress, improve bonding performance, and also further reduce the contact resistance of the electrode 10, thus improving the usability of the electrode 10.

[0045] In this embodiment, the tungsten content in the tungsten-doped diamond layer 13 is less than 20 at.%; this helps to ensure the corrosion resistance and wear resistance of the tungsten-doped diamond layer 13, and improves the service life of the electrode 10. Furthermore, the tungsten content in the tungsten-doped diamond layer 13 is greater than 5 at.% and less than 20 at.%; this helps to further reduce the contact resistance of the electrode 10, and further improve its wear resistance and corrosion resistance. Specifically, the tungsten content in the tungsten-doped diamond layer 13 can be, but is not limited to, 6 at.%, 7 at.%, 8.5 at.%, 9 at.%, 10 at.%, 12.8 at.%, 15 at.%, 17.2 at.%, or 19.5 at.%.

[0046] In this embodiment, the thickness of the tungsten-doped diamond-like carbon (TDLC) layer 13 is 0.3 μm-2 μm. This thickness of the TDLC layer 13 further ensures the wear resistance and corrosion resistance of the electrode 10, while also contributing to a reduction in contact resistance. Specifically, the thickness of the TDLC layer 13 can be, but is not limited to, 0.5 μm, 0.9 μm, 1 μm, 1.2 μm, 1.5 μm, 1.8 μm, or 2 μm. In one embodiment, the thickness of the TDLC layer 13 can be 0.5 μm-1 μm. In another embodiment, the thickness of the TDLC layer 13 can be 1 μm-2 μm.

[0047] In this embodiment, the thickness of the tungsten-doped diamond layer 13 is greater than or equal to the thickness of the tungsten carbide layer 12. This ensures the bonding performance of the tungsten-doped diamond layer 13 while simultaneously reducing the contact resistance of the electrode 10. In one embodiment, the thickness ratio of the tungsten-doped diamond layer 13 to the tungsten carbide layer 12 is 1-3. This improves the bonding strength of the tungsten-doped diamond layer 13 in the electrode 10, particularly the bonding strength between the tungsten carbide layer 12 and the tungsten-doped diamond layer 13 in the edge region of the electrode 10, and also helps to further reduce the contact resistance between the electrode 10 and the skin. Specifically, the thickness ratio of the tungsten-doped diamond layer 13 to the tungsten carbide layer 12 can be, but is not limited to, 1, 1.5, 1.8, 2, 2.3, 2.5, 2.7, or 3. Further, the thickness ratio of the tungsten-doped diamond layer 13 to the tungsten carbide layer 12 can be 1.5-3.

[0048] In this embodiment, the thickness of electrode 10 is 1 μm-5 μm. This thin electrode 10 allows for some flexibility, facilitating its adherence to the skin surface for use. Specifically, the thickness of electrode 10 can be, but is not limited to, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm, or 5 μm. In one embodiment, the thickness of electrode 10 can be 1 μm-3 μm. In another embodiment, the thickness of electrode 10 can be 2.5 μm-5 μm.

[0049] In this embodiment, the corrosion potential of electrode 10 is -200mV to -150mV, and the corrosion current density is 5×10⁻⁶ mV. -8 A / cm 2 -15×10 -8 A / cm 2 The impedance at 10Hz is 500Ω-1300Ω. Specifically, the corrosion potential of electrode 10 can be, but is not limited to, -200mV, -190mV, -180mV, -170mV, or -150mV, and the corrosion current density can be, but is not limited to, 5×10⁻⁶. -8 A / cm 2 8×10 -8 A / cm 2 10×10 -8 A / cm 2 13×10 -8 A / cm 2 Or 15×10 -8 A / cm 2 The impedance at 10Hz can be, but is not limited to, 500Ω, 600Ω, 800Ω, 1000Ω, 1200Ω, or 1300Ω. In one embodiment, the performance of the electrode 10 is the performance of the film layer formed by the underlayer 11, the tungsten carbide layer 12, and the tungsten-doped diamond-like carbon layer 13. In this embodiment, conductive adhesive is used to connect the wires to the substrate 14 of the electrode 10, and insulating adhesive is applied to the surface of the electrode 10, leaving a 1cm × 1cm electrode 10 area; electrochemical impedance spectroscopy and polarization curve testing are performed using an electrochemical workstation in an electrolytic cell (electrolyte is 0.9% physiological saline), with an Ag / AgCl electrode as the reference electrode.

[0050] The electrode 10 provided in this application has low impedance, excellent wear resistance and corrosion resistance, which improves the accuracy of detection and extends its service life, making it suitable for use in electronic equipment 300.

[0051] This application also provides a method for preparing an electrode 10, comprising: forming an underlayer 11, a tungsten carbide layer 12, and a tungsten-doped diamond-like carbon (TDLC) layer 13 by deposition, wherein the underlayer 11, the tungsten carbide layer 12, and the TDLC layer 13 are sequentially stacked to obtain the electrode 10. This preparation method is simple and convenient to operate, enabling the industrial production of the electrode 10. Furthermore, this method can produce the electrode 10 as described in any of the above embodiments, and the electrode 10 exhibits excellent electrochemical performance, which is beneficial for its use.

[0052] In this application, electrode 10 is prepared using a deposition method. In this embodiment, deposition includes at least one of physical vapor deposition (PVD) and chemical vapor deposition (CVD). Physical vapor deposition is a method of thin film deposition using physical mechanisms, while chemical vapor deposition utilizes gaseous or vaporous substances to react at the gas phase or gas-solid interface to generate solid deposits. In one embodiment, physical vapor deposition may include vacuum evaporation, sputtering, ion plating, etc. Specifically, sputtering may include DC sputtering, AC sputtering, reactive sputtering, and magnetron sputtering, etc., which can be further divided into balanced magnetron sputtering and unbalanced magnetron sputtering depending on the magnetic field configuration of the magnetron cathode. In another embodiment, chemical vapor deposition may include plasma chemical vapor deposition, thermochemical vapor deposition, photochemical vapor deposition, etc. Electrodes 10 prepared by the above deposition methods exhibit strong internal bonding and high reliability.

[0053] Please see Figure 7 Here is a flowchart of a method for preparing an electrode according to an embodiment of this application, including:

[0054] S101: Deposit the underlayer on the substrate surface.

[0055] S102: Deposit a tungsten carbide layer on the surface of the underlayer away from the substrate.

[0056] S103: A tungsten-doped diamond-like layer is deposited on the surface of the tungsten carbide layer away from the underlayer to obtain the electrode.

[0057] In this application, a substrate 14 is used as a carrier layer, and an underlayer 11, a tungsten carbide layer 12, and a tungsten-doped diamond-like carbon (TDLC) layer 13 are deposited on its surface to obtain the electrode 10. Specifically, the deposition method mentioned above can be used to prepare the underlayer 11, the tungsten carbide layer 12, and the tungsten-doped diamond-like carbon (TDLC) layer 13. In this embodiment, the substrate 14 is further cleaned before deposition. Further, a polishing process is performed before cleaning the substrate 14. Specifically, the substrate 14 can be electrochemically polished, and after polishing, it can be ultrasonically cleaned, such as for 15-20 minutes, in water or in an ethanol solution.

[0058] In this embodiment, the substrate 14 is further subjected to argon ion cleaning before deposition. Specifically, the surface of the substrate 14 is cleaned and the surface passivation film is removed by bombarding the surface with argon ions. In one embodiment of this application, the vacuum degree is less than or equal to 2.5 × 10⁻⁶. -5 The substrate 14 is bombarded under the conditions of a bias voltage of -300V to -700V. Further, the argon gas flow rate is 15 sccm-25 sccm, and the bombardment time is 10 min-35 min. Specifically, the argon gas flow rate can be, but is not limited to, 15 sccm, 18 sccm, 19 sccm, 20 sccm, 22 sccm, or 25 sccm, and the bombardment time can be, but is not limited to, 10 min, 15 min, 17 min, 20 min, 24 min, 25 min, 28 min, 30 min, or 33 min. In one embodiment, the vacuum degree is less than or equal to 2.5 × 10⁻⁶. -5 The substrate 14 was bombarded for 20-30 minutes under the following conditions: a bias voltage of -300V to -500V and an argon flow rate of 20-25 sccm.

[0059] In this application, the substrate 14 can rotate during the deposition process, thereby improving the uniformity of the film deposited on the surface of the substrate 14. In the embodiments of this application, the rotational speed of the substrate 14 can be 3 rpm / min to 10 rpm / min. Specifically, the rotational speed of the substrate 14 can be, but is not limited to, 3 rpm / min, 4 rpm / min, 5 rpm / min, 6 rpm / min, 7 rpm / min, 8 rpm / min, or 9 rpm / min, etc.

[0060] In this embodiment, the purity of the target material 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%. Even further, the purity of the target material used for deposition is greater than or equal to 99.99%. Using a target material with the above-mentioned purity can effectively avoid the influence of impurities on the performance of the electrode 10. In one embodiment, a chromium target can be used to prepare the underlayer 11; a tungsten target and graphite target, a tungsten carbide target, or a tungsten target and a gaseous carbon source (such as methane, acetylene, etc.) can be used to prepare the tungsten-doped diamond-like carbon layer 13; the purity of the above-mentioned target materials is greater than or equal to 99.9%.

[0061] In this embodiment of the application, the deposition pressure can be 4 × 10⁻⁶. -4 torr-9×10 -4 Specifically, the deposition pressure can be, but is not limited to, 4 × 10⁻⁶. -4 torr, 5×10 -4torr, 6×10 -4 torr, 7×10 -4 torr, 8×10 -4 torr or 9×10 -4 Torr, etc. In this embodiment, the flow rate of the inert gas during deposition is 15 sccm-30 sccm. Introducing inert gas during deposition prevents oxidation, maintains the deposition pressure, and allows for collisions with particles generated during deposition, thus affecting film deposition. Using the aforementioned flow rate of inert gas ensures a suitable deposition rate and the desired film morphology. Specifically, the flow rate of the inert gas during deposition can be, but is not limited to, 15 sccm, 17 sccm, 20 sccm, 23 sccm, 25 sccm, 28 sccm, or 30 sccm, and the inert gas can be, but is not limited to, argon. In this embodiment, a bias voltage is applied to the substrate 14 during deposition. Further, the bias voltage is -200V to 0. Further still, the bias voltage is -80V to -60V. Specifically, the bias voltage can be, but is not limited to, -80V, -75V, -70V, -65V, or -60V.

[0062] In step S101, a base layer 11 is first deposited on the substrate 14 to facilitate the bonding of the tungsten carbide layer 12 and the tungsten-doped diamond-like carbon layer 13. In this embodiment, magnetron sputtering is used to deposit the base layer 11. Further, unbalanced magnetron sputtering is used to deposit the base layer 11. In one embodiment of this application, magnetron sputtering is used to deposit the base layer 11 using a chromium target. This yields a chromium-containing base layer 11, i.e., a chromium layer. Further, the target power of the chromium target is 50W-1500W and / or the target current of the chromium target is 0.1A-10A. In one embodiment, the target power of the chromium target is 50W-1500W; that is, the chromium target can be mounted on an RF target position. In another embodiment, the target current of the chromium target is 0.1A-10A; that is, the chromium target can be mounted on a DC target position. In another embodiment, two chromium targets are provided, one mounted on the RF target position with a target power of 50W-1500W, and the other mounted on the DC target position with a target current of 0.1A-10A, thereby improving the fabrication efficiency. Specifically, the target power of the chromium target can be, but is not limited to, 100W, 300W, 500W, 750W, 900W, 1100W, or 1350W, and the target current of the chromium target can be, but is not limited to, 1A, 3A, 5A, 6A, 8A, or 10A. In the embodiments of this application, the deposition time for the underlayer 11 can be 30min-60min. Specifically, the deposition time for the underlayer 11 can be, but is not limited to, 30min, 35min, 40min, 45min, or 55min. In one embodiment, magnetron sputtering is used with a chromium target as the target material and an inert gas as the working gas to deposit the underlayer 11. The target power of the chromium target is 50W-1500W and / or the target current of the chromium target is 0.1A-10A, the flow rate of the inert gas is 15sccm-30sccm, and the deposition time is 20min-45min. Further, unbalanced magnetron sputtering is used to deposit the underlayer 11.

[0063] In S102, the bonding force of the tungsten-doped diamond-like carbon layer 13 is improved by setting the tungsten carbide layer 12, while the impedance of the electrode 10 is reduced. In this embodiment, the tungsten carbide layer 12 is formed by magnetron sputtering deposition. Further, the tungsten carbide layer 12 is formed by non-equilibrium magnetron sputtering deposition. In one embodiment of this application, the tungsten carbide layer 12 is formed by magnetron sputtering using a tungsten carbide target. Further, the target current of the tungsten carbide target is less than or equal to 10A. In one embodiment, the target current of the tungsten carbide target is 0.1A-10A. Specifically, the target current of the tungsten carbide target can be, but is not limited to, 1A, 2A, 5A, 7A, 8A, or 10A. In this embodiment, the deposition time of the tungsten carbide layer 12 can be 30min-60min. Specifically, the deposition time of the tungsten carbide layer 12 can be, but is not limited to, 30min, 35min, 40min, 45min, 50min, or 55min. In one embodiment of this application, during the deposition of the tungsten carbide layer 12, the target current of the tungsten carbide target gradually increases. Further, the target current of the tungsten carbide target gradually increases and then remains constant. Still further, the target current of the tungsten carbide target gradually increases and then remains constant, while the target current of the chromium target gradually decreases. This reduces internal stress and improves adhesion.

[0064] In S103, depositing a tungsten-doped diamond-like layer 13 on the surface of the tungsten carbide layer 12 helps to improve the bonding force of the tungsten-doped diamond-like layer 13. At the same time, the doping of tungsten reduces the internal stress of the tungsten-doped diamond-like layer 13, further improving the stability of the structure.

[0065] In this embodiment, a tungsten-doped diamond-like carbon (TDLC) layer 13 is deposited using magnetron sputtering. Further, an unbalanced magnetron sputtering method is used to deposit the TDLC layer 13. In one embodiment, magnetron sputtering is used to deposit the TDLC layer 13 using a tungsten carbide target and a graphite target. Further, the target current of the tungsten carbide target is gradually decreased, while the target current of the graphite target is gradually increased to 0.1A-10A, which can further alleviate internal stress and improve adhesion. Further still, the target current of the tungsten carbide target is gradually decreased to 0.1A-1.5A. Specifically, the target current of the graphite target can be, but is not limited to, increased to 0.5A, 2A, 5A, 7A, 8A, or 10A. In another embodiment, magnetron sputtering is used to deposit the TDLC layer 13 using a tungsten carbide target as the target material and a gaseous carbon source as the working gas. Furthermore, the target current of the tungsten carbide target is gradually reduced to 0.1A-5A, and the flow rate of the gaseous carbon source is 5sccm-30sccm, which can further alleviate internal stress and improve adhesion. Specifically, the flow rate of the gaseous carbon source can be, but is not limited to, 5sccm, 10sccm, 15sccm, 20sccm, 25sccm, or 30sccm. In the embodiments of this application, the deposition time of the tungsten-doped diamond-like carbon layer 13 can be 30min-150min. Specifically, the deposition time of the tungsten-doped diamond-like carbon layer 13 can be, but is not limited to, 30min, 50min, 60min, 90min, 100min, 120min, or 150min.

[0066] In this application, the sputtering power supply can be a DC power supply or an RF power supply, selected according to specific needs. In one embodiment, the RF power supply power can be 50W-600W. Specifically, the RF power supply power can be, but is not limited to, 50W, 100W, 200W, 300W, 400W, 500W, or 600W, etc.

[0067] Understandably, this application describes the preparation method of electrode 10 using magnetron sputtering deposition as an example. Of course, other physical vapor deposition or chemical vapor deposition methods can also be used to prepare the electrode 10, which consists of the underlayer 11, tungsten carbide layer 12 and tungsten-doped diamond-like layer 13 protected in this application. These are also within the scope of protection of this application.

[0068] Please see Figure 8 The flowchart illustrates a method for fabricating the main body of an electronic device according to an embodiment of this application, including:

[0069] S201: Deposit the underlayer on the shell surface.

[0070] S202: Deposit a tungsten carbide layer on the surface of the underlayer away from the substrate.

[0071] S203: A tungsten-doped diamond-like layer is deposited on the surface of the tungsten carbide layer away from the underlayer to obtain the main body of the electronic device.

[0072] In this application, the electronic device body 10 can be fabricated simultaneously using the above-described preparation method to prepare the electrode 10. By using the housing 20 as a support layer, the use of the substrate 14 is avoided, reducing preparation costs. Simultaneously, the electronic device body 100 can be directly fabricated, improving preparation efficiency. Furthermore, the electrode 10 is directly formed on the housing 20, which helps improve the bonding force between the electrode 10 and the housing 20, ensuring the reliability of the electronic device body 100. The deposition processes of the underlayer 11, tungsten carbide layer 12, and tungsten-doped diamond-like carbon layer 13 in S201, S202, and S203 can be referred to the descriptions in S101, S102, and S103 above. The treatment of the housing 20 can be referred to the treatment of the substrate 14 in S101 above, and will not be repeated here. In this embodiment, a protective layer is also provided on the surface of the housing 20 before depositing the underlayer 11. By providing a protective layer on the surface of the housing 20, areas where electrode 10 does not need to be deposited are protected. Specifically, a pre-deposition area is formed by providing a protective layer on the surface of the housing 20.

[0073] The effects of the electrodes provided in this application will be further illustrated below through specific embodiments.

[0074] Example 1

[0075] Electrodes were fabricated using an unbalanced magnetron sputtering coating system. The stainless steel substrate was cleaned, dried, and then placed in the coating system. Chromium, tungsten carbide, and graphite targets were installed on the RF, DC, and DC target positions, respectively. The purity of the chromium, tungsten carbide, and graphite targets was 99.9%.

[0076] After clamping the target and stainless steel substrate, close the sealing cap and evacuate the deposition chamber to a vacuum level of 2.5 × 10⁻⁶. -5 With a substrate bias voltage of -500V, the stainless steel substrate surface was bombarded with argon ions (argon flow rate of 20 sccm) for 25 min. The substrate bias voltage was then adjusted to -100V, and the chromium target power was increased to 1200W for 60 min, forming a chromium layer on the stainless steel substrate surface. The substrate bias voltage was then adjusted to -80V, and the chromium target power was gradually reduced to 0, while the tungsten carbide target current was gradually increased to 5A and maintained for 30 min, forming a tungsten carbide layer on the chromium layer surface. Finally, the substrate bias voltage was adjusted to -60V, and the tungsten carbide target current was gradually reduced to 1A. The graphite target current was then gradually increased to 5A and maintained for 30 min, forming a tungsten-doped diamond-like carbon layer on the tungsten carbide layer surface, resulting in the electrode. The total thickness of the coating on the stainless steel substrate surface was 1.7 μm.

[0077] Please see Figure 9 The image shown is an electron microscope (EM) image of the surface morphology of the tungsten-doped diamond-like layer in the electrode prepared in Example 1. The scale bar is 10 μm. Please refer to [link / reference]. Figure 10 The image shown is an electron microscope (EM) image of the cross-section of the electrode prepared in Example 1, with a scale bar of 3 μm. It can be seen that the layers in the electrode are tightly bonded without any detachment. Elemental analysis of the longitudinal section of the prepared electrode was performed using energy dispersive spectroscopy (EDS). The tungsten-doped diamond-like carbon layer contained 91.6 at.% carbon, 7.7 at.% tungsten, and 0.7 at.% chromium. The tungsten carbide layer contained 76.4 at.% carbon, 21.4 at.% tungsten, and 2.2 at.% chromium. The EDS method can lead to the inclusion of some chromium in the tungsten-doped diamond-like carbon layer and the tungsten carbide layer during testing; therefore, chromium was detected in both layers.

[0078] Example 2

[0079] Electrodes were prepared using an unbalanced magnetron sputtering coating system. The stainless steel substrate was cleaned and dried before being placed in the coating system. Chromium and tungsten carbide targets were installed on DC target positions. The purity of the chromium and tungsten carbide targets was 99.9%.

[0080] After clamping the target and stainless steel substrate, close the sealing cap and evacuate the deposition chamber to a vacuum level of 2.5 × 10⁻⁶. -5 With a substrate bias voltage of -550V, the stainless steel substrate surface was bombarded with argon ions (argon flow rate of 20 sccm) for 30 min. The stainless steel substrate bias voltage was then adjusted to -80V, and the target current of the chromium target was increased to 6A for 40 min, forming a chromium layer on the stainless steel substrate surface. The stainless steel substrate bias voltage was then adjusted to -60V, and the target power of the chromium target was gradually reduced to 0, while the target current of the tungsten carbide target was gradually increased to 5A and maintained for 60 min, forming a tungsten carbide layer on the chromium layer surface. The target current of the tungsten carbide target was gradually reduced to 1A, and acetylene gas (flow rate of 20 sccm) was introduced. The RF source power was increased to 500W, and the deposition time was 12 min, forming a tungsten-doped diamond-like carbon layer on the tungsten carbide layer surface, thus obtaining the electrode. The total thickness of the coating on the stainless steel substrate surface was 1.2 μm.

[0081] Please see Figure 11 The image shown is an electron microscope (EM) image of the surface morphology of the tungsten-doped diamond-like layer in the electrode prepared in Example 2. The scale bar is 1 μm. Please refer to [link / reference]. Figure 12The image shown is an electron microscope (EM) image of the cross-section of the electrode prepared in Example 2, with a scale bar of 1 μm. It can be seen that the layers in the electrode are tightly bonded without any detachment. Elemental analysis of the longitudinal section of the prepared electrode was performed using energy dispersive spectroscopy (EDS). The tungsten-doped diamond-like carbon layer contained 88.7 at.% carbon, 10.8 at.% tungsten, and 0.5 at.% chromium, while the tungsten carbide layer contained 64.2 at.% carbon, 33.3 at.% tungsten, and 2.5 at.% chromium.

[0082] Example 3

[0083] The difference from Example 1 is that the target current of the tungsten carbide target is directly reduced to 1A and remains unchanged when the tungsten-doped diamond-like layer is deposited.

[0084] Example 4

[0085] An electrode includes a substrate, a chromium layer, a tungsten carbide layer, and a tungsten-doped diamond-like carbon layer stacked together. The thickness of the chromium layer is 0.1 μm, the thickness of the tungsten carbide layer is 0.7 μm, and the thickness of the tungsten-doped diamond-like carbon layer is 0.7 μm.

[0086] Example 5

[0087] An electrode includes a substrate, a chromium layer, a tungsten carbide layer and a tungsten-doped diamond-like carbon layer stacked together, wherein the thickness of the chromium layer is 0.1 μm, the thickness of the tungsten carbide layer is 0.7 μm, and the thickness of the tungsten-doped diamond-like carbon layer is 2 μm.

[0088] Example 6

[0089] An electrode includes a substrate, a chromium layer, a tungsten carbide layer and a tungsten-doped diamond-like carbon layer stacked together, wherein the thickness of the chromium layer is 0.1 μm, the thickness of the tungsten carbide layer is 1.5 μm, and the thickness of the tungsten-doped diamond-like carbon layer is 0.7 μm.

[0090] Comparative Example 1

[0091] An electrode includes a substrate, a chromium layer, and a tungsten-doped diamond-like layer stacked together.

[0092] Comparative Example 2

[0093] An electrode includes a substrate, a chromium layer, a tungsten carbide layer and a diamond-like carbon layer stacked together.

[0094] Comparative Example 3

[0095] An electrode includes a substrate, a tungsten carbide layer, and a tungsten-doped diamond-like layer stacked together.

[0096] The electrodes prepared in Examples 1-6 and Comparative Examples 1-2 were tested. The film layer on the substrate surface of the electrode prepared in Comparative Example 3 was prone to peeling off, failing to meet the usage requirements, and was therefore not tested. X-ray diffraction was performed on the prepared electrodes; please refer to [reference needed]. Figure 13 The figures show the X-ray diffraction patterns of the electrodes prepared in Examples 1 and 2, where characteristic diffraction peaks of tungsten carbide are observed at the 2θ angle near 42° and around 36°. Under conditions of a load of 200 mN, a wear track length of 4 mm, and a wear time of 10 min, the tribological properties of the tungsten-doped diamond-like carbon (TDLC) layer of the electrode were tested using a UMT-3 tribological testing machine. The wear track morphology was measured using a white light interferometer, and the wear resistance was determined based on the depth and width of the wear track. Please refer to [link to relevant documentation]. Figure 14 and Figure 15 The figures show the results of friction coefficient and wear trace detection on the electrode surfaces prepared in Examples 1 and 2. It can be seen that the friction coefficient of the electrode surface is very low, and the wear traces are small, indicating excellent wear resistance of the electrode. For Raman spectroscopy analysis of the tungsten-doped diamond-like layer surface of the electrode, please refer to [link to relevant documentation]. Figure 16 and Figure 17 The image shows the Raman spectra of the tungsten-doped diamond-like layer surface of the electrodes prepared in Examples 1 and 2, at 1300 cm⁻¹. -1 The nearby D peak and 1560cm -1 The G peak in the vicinity is a Raman characteristic peak of carbon atom crystal, the D peak represents defects in the carbon atom lattice, and the G peak represents the sp atoms of carbon atoms. 2 Hybrid in-plane stretching vibration, the ratio of the peak areas of the D peak and the G peak (A) D / A G The larger the value, the higher the value of sp. 2 The higher the content and the smaller the peak area ratio, the better the sp content. 3 The higher the content; among them, A in the Raman spectrum of Example 1 D / A G The value is 7.53, and A in the Raman spectrum of Example 2 is... D / A G The value is 6.12. Electrochemical impedance spectroscopy and polarization curve analysis were performed on the electrode in 0.9% physiological saline (Ag / AgCl electrode was used as the reference electrode). Please refer to [link to documentation]. Figure 18 and Figure 19 The figures show the AC impedance spectra of the electrodes prepared in Examples 1 and 2. The electrode prepared in Example 1 has an impedance of 581Ω at 10Hz, a corrosion potential of -192mV, and a corrosion current density of 1.44×10⁻⁶. -7 A / cm 2 The electrode prepared in Example 2 has an impedance of 1170Ω at 10Hz, a corrosion potential of -168mV, and a corrosion current density of 5.44×10⁻⁶. -8 A / cm 2Furthermore, the impedance of the electrodes obtained in Examples 1-6 is lower than that of the electrodes obtained in Comparative Examples 1-2. The impedance of the electrode obtained in Example 1 is lower than that of the electrode obtained in Example 3, and the impedance of the electrodes obtained in Examples 4-5 is lower than that of the electrode obtained in Example 6. Meanwhile, the electrode obtained in Comparative Example 2 exhibits reduced toughness and is prone to peeling. It can be seen that the electrodes provided in this application have low impedance, high corrosion resistance, and excellent wear resistance, which is beneficial for use in electronic devices.

[0097] The above provides a detailed description of the embodiments provided in this application. This document elucidates and explains the principles and implementation methods of this application. The above description is only intended to help understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. An electrode, characterized in that, It includes a base layer, a tungsten carbide layer, and a tungsten-doped diamond layer stacked in sequence; along the direction from the tungsten carbide layer to the tungsten-doped diamond layer, the tungsten content in the tungsten-doped diamond layer gradually decreases.

2. The electrode as described in claim 1, characterized in that, The thickness of the tungsten-doped diamond-like layer is greater than or equal to the thickness of the tungsten carbide layer.

3. The electrode as described in claim 1, characterized in that, The tungsten content in the tungsten-doped diamond-like layer is less than 20 at.%.

4. The electrode as described in claim 1, characterized in that, The thickness ratio of the tungsten-doped diamond-like layer to the tungsten carbide layer is 1-3.

5. The electrode as claimed in claim 1, characterized in that, The thickness of the base layer is 0.1μm-2μm; The thickness of the tungsten carbide layer is 0.1 μm-2 μm; The thickness of the tungsten-doped diamond-like layer is 0.3 μm-2 μm; The thickness of the electrode is 1μm-5μm.

6. The electrode as claimed in claim 1, characterized in that, The base layer material includes chromium.

7. The electrode as claimed in claim 1, characterized in that, The corrosion potential of the electrode is -200mV to -150mV, and the corrosion current density is 5×10⁻⁶ mV. -8 A / cm 2 -15×10 -8 A / cm 2 The impedance at 10Hz is 500Ω-1300Ω.

8. A method for preparing an electrode, characterized in that, include: An electrode is formed by deposition of an underlayer, a tungsten carbide layer, and a tungsten-doped diamond-like carbon (TDLC) layer, which are stacked sequentially to form an electrode. The tungsten content in the TDLC layer gradually decreases along the direction from the tungsten carbide layer to the tungsten-doped diamond-like carbon (TDLC) layer.

9. The preparation method according to claim 8, characterized in that, The tungsten carbide layer is formed by deposition, which includes: using magnetron sputtering to deposit the tungsten carbide layer with a tungsten carbide target as the target material, wherein the target current of the tungsten carbide target is less than or equal to 10A. The tungsten-doped diamond-like carbon (TDLC) layer is formed by deposition methods including: using magnetron sputtering to deposit the TDLC layer with a tungsten carbide target and a graphite target as target materials, wherein the target current of the tungsten carbide target is gradually reduced and the target current of the graphite target is gradually increased to 0.1A-10A; or using magnetron sputtering to deposit the TDLC layer with a tungsten carbide target as target material and a gaseous carbon source as working gas, wherein the target current of the tungsten carbide target is gradually reduced to 0.1A-5A and the flow rate of the gaseous carbon source is 5sccm-30sccm.

10. An electronic device, characterized in that, It includes an electronic device body, the electronic device body including electrodes, the electrodes being the electrodes according to any one of claims 1-7.

Images