Multi-physical field regulation graphene electrode preparation method and device and array device

Abstract

The invention discloses a multi-physical field regulation graphene electrode preparation method and device and an array device, and relates to the technical field of electrode materials. The multi-physical field regulation and control graphene electrode preparation device comprises a base, a laser generation device, a temperature field device, an ultrasonic generation device, an electric field generation device and a magnetic field generation device, and the temperature field device is used for generating a temperature gradient with the temperature gradually reduced from the upper surface of the temperature field device to the upper part; the electric field generating device is used for generating a pulse electric field in the vertical direction and synchronous with the laser beam frequency, the magnetic field generating device is used for generating a magnetic field orthogonal to the pulse electric field, and the ultrasonic generating device is used for generating ultrasonic waves synchronous with the moving path of the laser beam. Based on a laser-induced graphene technology, the quality and performance of the graphene electrode are improved through multi-physical field regulation and control.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of electrode materials, in particular to a multi-physical field regulation graphene electrode preparation method and device and array device. BACKGROUND

[0002] Laser-induced graphene is generated by using high-energy laser beams to interact with carbon source precursors (high-molecular polymers, natural organic matter, etc.), through localized high-temperature pyrolysis and graphitization processes, directly on the surface or inside of the material. In the field of electrode preparation of array devices, laser-induced graphene electrodes have the advantages of simple and efficient operation, no need for complex chemical reagents, and can be directly prepared in situ on various substrates, etc. They provide an innovative path for the low-cost and large-scale preparation of high-performance electrodes, and help to solve the problems of pollution, complicated steps, high cost, etc. in traditional electrode preparation processes. They have important scientific value and application prospects for promoting technological innovation in the fields of energy storage, sensors, flexible electronics, etc.

[0003] However, the quality and performance of graphene electrodes prepared by traditional laser-induced graphene technology are limited, and there are the following core problems: first, during the pyrolysis process, the carbon source precursors cannot be effectively replenished, the supply of carbon atoms in the laser action area is uneven, and structural defects such as vacancies and edges are easily formed. At the same time, the natural cooling rate after laser scanning is relatively fast, and the thermal stress concentration easily causes the graphene layer to crack, reducing the electrode density. Second, the carbon atom plasma generated by picosecond laser induction diffuses without constraint, the energy utilization rate is low, and the carbon atoms are randomly stacked on the substrate surface, making it difficult to accurately control the number of graphene layers, resulting in poor uniformity of the electrode electrical performance. Third, the interlayer van der Waals force of graphene generated by carbon source pyrolysis is strong, and it is easy to stack into a dense structure, lacking three-dimensional interconnected pores, which limits the specific surface area and flexibility of the electrode, and cannot meet the demand of flexible electronic devices for the mechanical properties of the electrode. Fourth, the traditional technology does not regulate the direction of carbon atom migration, and the carbon atoms generated by pyrolysis easily diffuse horizontally, resulting in poor vertical stacking of the graphene layer and the substrate, weak interfacial bonding force, and increased contact resistance between the electrode and the substrate. SUMMARY

[0004] The present application provides a multi-physical field regulation graphene electrode preparation method and device and array device, which uses laser-induced graphene technology to prepare graphene electrodes, aiming to improve the quality and performance of graphene electrodes through multi-physical field synergistic regulation.

[0005] The multi-physical field regulation graphene electrode preparation device provided by the present application comprises a base, a laser generating device, a temperature field device, an ultrasonic generating device, an electric field generating device and a magnetic field generating device.

[0006] The laser generating device is used to generate laser beams that can induce carbon source precursors to generate graphene.

[0007] The temperature field device is arranged on the base and is configured to generate a temperature gradient gradually decreasing upwards from an upper surface of the temperature field device;

[0008] The electric field generating device comprises an upper electrode plate and a lower electrode plate, the lower electrode plate is arranged on the upper surface of the temperature field device, and the upper electrode plate is arranged in parallel above the lower electrode plate, the electric field generating device is configured to generate a vertical direction pulse electric field between the upper electrode plate and the lower electrode plate, and the pulse electric field is synchronized with the frequency of the laser beam;

[0009] The magnetic field generating device is arranged on the side surface of the temperature field device and is configured to generate a magnetic field orthogonal to the vertical direction pulse electric field;

[0010] The ultrasonic generating device is configured to generate ultrasonic waves synchronized with the movement path of the laser beam.

[0011] The application provides a multi-physical field regulated graphene electrode preparation method, and the graphene electrode is prepared by using the device.

[0012] S1, a carbon source precursor is covered on the surface of a device to be processed, and the carbon source precursor is a polymer containing a polar group;

[0013] S2, laser parameters of a laser generating device are set, and processing parameters of a temperature field device, an ultrasonic generating device, an electric field generating device and a magnetic field generating device are set;

[0014] S3, the device to be processed covered with the carbon source precursor is arranged on the lower electrode plate of the electric field generating device, and the laser generating device, the temperature field device, the ultrasonic generating device, the electric field generating device and the magnetic field generating device are started, so that the laser beam emitted by the laser generating device is irradiated on the carbon source precursor according to a preset scanning path;

[0015] S4, after the laser scanning is completed, the device to be processed is cooled at a preset cooling rate, the carbon source precursor is cut by the laser, and the uncarbonized region of the carbon source precursor is removed, so that a patterned graphene electrode is obtained.

[0016] Optionally, the carbon source precursor is a polyimide.

[0017] Optionally, the laser parameters comprise the following: outputting a picosecond laser, a defocusing amount of 5-8 mm, a laser frequency of 200-400 kHz, a laser pulse width of 2-8 ps, a laser scanning speed of 100-400 mm / s, and a laser power of 1-4 W.

[0018] Optionally, the processing parameter of the electric field generating device comprises: outputting a pulse electric field, the pulse width of the pulse electric field is 1-5 ps, the frequency is 200 kHz-400 kHz, and the intensity is 50-200 V / cm.

[0019] Optionally, the processing parameter of the magnetic field generating device comprises: the magnetic field intensity of the region where the device to be processed is located is 0.8-1.2 T.

[0020] Optionally, the ultrasonic wave generated by the ultrasonic generating device has a frequency of 20-40 kHz and a power of 80-150 W.

[0021] Optionally, the processing parameter of the temperature field device comprises: the temperature of the upper surface of the temperature field device is set to 300-350 DEG C, and the preset cooling rate is set to 2-5 DEG C / min.

[0022] The application further provides a graphene electrode prepared by the above device or preparation method, which is suitable for various flexible substrate devices or rigid substrate devices.

[0023] The application further provides an array device, which comprises a substrate and a plurality of array elements arranged on the substrate, and the array elements are connected with the graphene electrode prepared by the above device or preparation method.

[0024] The application has the following beneficial effects:

[0025] The technical scheme for preparing the graphene electrode in the application is based on laser-induced graphene technology, and the quality and performance of the graphene electrode are improved through multi-physical field regulation: first, the temperature field device generates a gradient temperature field in the thickness direction of the carbon source precursor, drives the carbon source molecular chain to migrate from the bottom interface of the carbon source precursor cover layer to the surface subjected to laser action, effectively supplements the carbon atom source in the laser processing area, avoids uneven supply of the carbon source, reduces structural defects such as vacancies and edges, and the temperature field device can also control the cooling rate of the device to be processed, so as to avoid cracking of the graphene electrode caused by thermal stress;

[0026] Second, the horizontal diffusion of carbon atom plasma is constrained by the orthogonal magnetic field and electric field, the diffusion radius of the carbon atom plasma is reduced, the number of graphene layers is accurately controlled, and the uniformity of the graphene electrode is improved; at the same time, the high-energy plasma is constrained in a small area controlled accurately, the energy localization is enhanced, and the laser energy utilization rate is optimized.

[0027] Third, the ultrasonic generating device generates micro-jet flow through ultrasonic cavitation effect, which can break the local steep temperature gradient of carbon source pyrolysis, improve the uniformity of graphene growth, and at the same time, ultrasonic vibration reduces the van der Waals force between graphene layers, forms three-dimensional interconnected pores in the graphene electrode, and increases the specific surface area of the graphene electrode.

[0028] Fourthly, the electric field generating device drives the vertical migration of carbon atoms by exerting force on the polar groups in the carbon source precursor through the vertical direction pulse electric field, inhibits the horizontal diffusion of carbon atoms, can promote the vertical stacking of graphene layers, and improves the bonding force between the graphene electrode and the interface of the device to be processed, and reduces the contact resistance. BRIEF DESCRIPTION OF DRAWINGS

[0029] In order to more clearly illustrate the technical solutions in the embodiments of the present application or the prior art, the drawings needed to be used in the embodiments or prior art description will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can be obtained by those skilled in the art without creative labor.

[0030] Figure 1 It is a three-dimensional structure schematic diagram of some embodiments of the present application multi-physical field regulation graphene electrode preparation device.

[0031] Figure 2 It is a front view of some embodiments of the present application multi-physical field regulation graphene electrode preparation device.

[0032] Figure 3 It is a flow chart of some embodiments of the present application multi-physical field regulation graphene electrode preparation method.

[0033] Figure 4 It is a flow chart of preparing a graphene electrode of an array device in embodiment 1 of the present application.

[0034] Figure 5 It is a comparison schematic diagram before and after removing the excess carbon source precursor of the array device prepared in embodiment 1 of the present application.

[0035] Figure 6 It is a Raman spectrum of the graphene electrode prepared in embodiment 1 of the present application.

[0036] Figure 7 It is a SEM diagram of the graphene electrode prepared in embodiment 1 of the present application.

[0037] Explanation of reference signs:

[0038] 1, base; 2, laser beam; 3, temperature field device; 4, electric field generating device; 4-1, lower electrode plate; 4-2, upper electrode plate; 5, magnetic field generating device; 6, ultrasonic generating device; 7, support rod; 8, glass substrate; 100, device array; 200, carbon source precursor; 300, graphene electrode. DETAILED DESCRIPTION

[0039] To make the objectives, features, and advantages of this invention more apparent and understandable, the technical solutions of the embodiments of this invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the embodiments described below are only some embodiments of this invention, and not all embodiments. Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0040] In the description of this invention, it should be understood that the terms "center", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the accompanying drawings. They are only for the convenience of describing this invention and simplifying the description, and do not indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limitations on this invention.

[0041] See Figure 1 , 2 The multi-physics field controlled graphene electrode preparation device provided in this embodiment of the invention includes a base 1, a laser generating device (the specific device is omitted in the figure, and the laser beam 2 represents the function of the laser generating device), a temperature field device 3, an electric field generating device 4, a magnetic field generating device 5, and an ultrasonic generating device 6.

[0042] Among them, the laser generating device is used to generate a laser beam 2 that can induce the formation of graphene from carbon source precursors;

[0043] A temperature field device 3 is mounted on a base 1 and is used to generate a temperature gradient that gradually decreases in temperature from the upper surface of the temperature field device 3 upwards. An electric field generating device 4 includes an upper electrode plate 4-2 and a lower electrode plate 4-1. The lower electrode plate 4-1 is mounted on the upper surface of the temperature field device 3, and the upper electrode plate 4-2 is arranged parallel to the upper surface of the lower electrode plate 4-1. The electric field generating device 4 is used to generate a vertical pulsed electric field between the upper electrode plate 4-2 and the lower electrode plate 4-1. The pulsed electric field is synchronized with the frequency of the laser beam. A magnetic field generating device 5 is mounted on the side of the temperature field device 3 and is used to generate a magnetic field orthogonal to the vertical pulsed electric field. An ultrasonic generating device 6 is used to generate ultrasonic waves synchronized with the movement path of the laser beam.

[0044] In the embodiment of the present application, the sample to be processed (carbon source precursor or device covered with carbon source precursor) is placed on the lower electrode plate 4-1, and the laser beam 2 generated by the laser generating device is irradiated on the sample to be processed, so that the target area of the carbon source precursor is graphitized to generate a graphene electrode; the laser generating device can be a picosecond laser, and the laser pulse generated by the picosecond laser has a duration of picoseconds, and the energy is concentrated on the carbon source precursor in a very short time, so that the graphene structure can be accurately controlled, the processing precision is high, and the device integration process is simplified.

[0045] The temperature field device 3 can be a programmed temperature heating table to accurately control the temperature of the heating table surface and the heating rate and constant temperature time; in some other embodiments, the temperature field device can also be a semiconductor heating sheet, an infrared heating lamp array or other heating devices to meet specific needs.

[0046] The ultrasonic generating device 6 can be an ultrasonic transducer connected with an ultrasonic probe, the ultrasonic transducer generates high-frequency signals and emits ultrasonic waves through the ultrasonic probe to directly act on the sample to be processed, and the ultrasonic generating device or the ultrasonic probe can be clamped by a mechanical arm, and the moving path thereof is kept synchronous with the laser beam.

[0047] The electric field generating device 4 includes a high-voltage pulse power supply and a lower electrode plate 4-1 and an upper electrode plate 4-2 connected with the high-voltage pulse power supply, and the high-voltage pulse power supply can output a pulse voltage with a pulse width of picoseconds.

[0048] The magnetic field generating device 5 can be a permanent magnet device, an electromagnetic coil device (Helmholtz coil, solenoid coil, etc.) or a superconducting magnet device, which is used to generate a uniform and controllable magnetic field orthogonal to the direction of the pulse electric field applied between the upper and lower electrode plates.

[0049] In some embodiments, the upper electrode plate 4-2 is a transparent electrode plate, and the laser generating device is arranged above the upper electrode plate 4-2, and the laser beam 2 emitted by the laser generating device can pass through the transparent upper electrode plate 4-2 to act on the sample to be processed.

[0050] In some embodiments, the multi-physical field regulated graphene electrode preparation device further includes a plurality of supporting rods 7; the plurality of supporting rods 7 are used to connect the upper electrode plate 4-2 and the lower electrode plate 4-1 to support the upper electrode plate 4-2.

[0051] The multi-physical field regulated graphene electrode preparation device provided by the embodiment of the present application aims to provide multi-physical field regulation to the process of laser-induced preparation of a graphene electrode through a temperature field device, an ultrasonic generating device, an electric field generating device and a magnetic field generating device, so as to improve the quality and performance of the graphene electrode.

[0052] Reference Figure 3The method for preparing the graphene electrode by using the graphene electrode preparation device with multi-physical field regulation provided in the above embodiment is as follows, comprising steps S1-S4.

[0053] S1, covering the carbon source precursor on the surface of the device to be processed; the carbon source precursor is a polymer containing a polar group.

[0054] Specifically, the carbon source precursor includes but is not limited to polyimide (PI), polyetherimide (PEI), phenolic resin (PF), polybenzimidazole (PBI), polyether sulfone (PES), polyacrylonitrile (PAN), polylactic acid (PLA), phenolic resin, lignocellulose and the like polymer; in the process of laser-induced pyrolysis of the carbon source, the polar group in the carbon source precursor can promote the migration of carbon atoms in the vertical direction under the action of the vertical pulsed electric field, and inhibit the horizontal thermal diffusion of carbon atoms.

[0055] In some preferred embodiments, the carbon source precursor is polyimide, the polar axis of the imide group in the polyimide is consistent with the thickness direction of the polyimide film (vertical orientation), and the electric field force generated by the vertical pulsed electric field can exert a directional effect on the polyimide molecules in the vertical direction, thereby directionally driving the carbon atoms to be orderly stacked in the direction perpendicular to the substrate of the device to be processed.

[0056] In the embodiments of the present application, the device to be processed includes but is not limited to flexible substrate devices (such as polymer substrate devices, textile / fiber devices, etc.) and rigid substrate devices (such as metal substrate devices, ceramic substrate devices, glass substrate devices, etc.).

[0057] S2, setting the laser parameters of the laser generating device, and setting the processing parameters of the temperature field device, the ultrasonic generating device, the electric field generating device and the magnetic field generating device.

[0058] Specifically, the laser generating device is used to generate a laser beam that can induce the carbon source precursor to generate graphene.

[0059] In some preferred embodiments, the laser generating device is a picosecond laser with an output wavelength of 515 nm, and the laser parameters are set as follows: defocusing amount 5-8 mm, laser frequency 200-400 kHz, laser pulse width 2-8 ps, scanning speed 100-400 mm / s, and laser power 1-4 W.

[0060] The temperature field device is used to generate a temperature gradient gradually decreasing upwards from the upper surface of the temperature field device, and the temperature gradient can drive the carbon source precursor molecular chain to migrate from the bottom interface of the carbon source precursor covering layer (the interface of the carbon source precursor close to the device substrate to be processed) to the surface subjected to laser action, effectively supplementing the carbon atom source of the laser processing area, avoiding uneven supply of the carbon source, reducing structural defects such as vacancies and edges, and the temperature field device can also control the cooling rate of the device to be processed, reducing the risk of cracking of the graphene electrode caused by thermal stress.

[0061] In some preferred embodiments, the processing parameters of the temperature field device are set as follows: the temperature of the upper surface of the temperature field device is set to 300-350℃, and the preset cooling rate after preparing the graphene electrode is set to 2-5℃ / min.

[0062] The ultrasonic generating device is used to generate ultrasonic waves synchronized with the movement path of the laser beam, and the ultrasonic direction is consistent with the scanning direction of the laser beam. When the laser acts on the carbon source precursor, the ultrasonic waves propagate in the carbon source precursor in the laser action area to induce micro cavitation bubbles, and the cavitation bubbles collapse asymmetrically near the phase interface to convert the ultrasonic energy into the kinetic energy of directional fluid, that is, the ultrasonic generating device can generate micro jets through the ultrasonic cavitation effect to break the local steep temperature gradient (including surface temperature and deep temperature) of carbon pyrolysis, thereby improving the uniformity of graphene growth. At the same time, ultrasonic vibration can reduce the van der Waals force between graphene layers, and form three-dimensional interconnected pores in the graphene electrode to increase the specific surface area of the graphene electrode.

[0063] In some preferred embodiments, the ultrasonic generating device generates ultrasonic waves with a frequency of 20kHz-40kHz and a power of 80-150W.

[0064] The electric field generating device is used to generate a vertical direction pulse electric field between the upper and lower electrode plates, and the pulse electric field is synchronized with the frequency of the laser beam. The vertical direction pulse electric field drives the carbon atoms to migrate in the vertical direction of the device substrate by applying an electric field to the polar groups on the carbon source precursor molecular chain, thereby inhibiting the horizontal thermal diffusion of carbon atoms, promoting the ordered stacking of graphene in the vertical direction, improving the bonding force between the graphene electrode and the interface of the device to be processed, and reducing the contact resistance. In addition, the pulse electric field with the same frequency as the laser avoids excessive polarization or damage to the carbon source precursor molecular chain caused by continuous high energy accumulation.

[0065] In some preferred embodiments, the processing parameters of the electric field generating device are set as follows: the pulse width of the pulse electric field between the upper and lower electrode plates is 1-5ps, the frequency is 200kHz-400kHz, and the intensity is 50-200V / cm.

[0066] The magnetic field generating device is used for generating a magnetic field which is orthogonal to the pulsed electric field in the vertical direction, and the magnetic field direction is orthogonal to the pulsed electric field (i.e., parallel to the device substrate plane), and the laser-induced carbon atom plasma is constrained by the Lorentz force in the magnetic field, so that the diffusion radius of the carbon atom plasma can be reduced; at the same time, the orthogonal configuration of the magnetic field and the pulsed electric field forms an “electromagnetic guide”, so that the carbon atom plasma is preferentially stacked in the center area of the laser spot (the area with the highest energy density), and the number of graphene layers can be more accurately controlled; in addition, the electromagnetic field constrains the high-energy plasma in a small area which is accurately controlled, enhances the energy localization, optimizes the energy utilization rate, and the laser energy utilization rate can be increased by 20-40%.

[0067] In some preferred embodiments, the processing parameters of the magnetic field generating device are set as follows: the magnetic field strength in the area where the device to be processed is located is 0.8-1.2T.

[0068] S3, the device to be processed covered with the carbon source precursor is placed on the lower electrode plate of the electric field generating device, the laser generating device, the temperature field device, the ultrasonic generating device, the electric field generating device and the magnetic field generating device are started, and the laser beam emitted by the laser generating device is irradiated on the carbon source precursor according to the preset scanning path.

[0069] In the embodiments of the present application, the pattern of the graphene electrode includes but is not limited to straight lines, serpentine, interlocking, fractals and the like, and the scanning path of the laser beam is set according to the pattern of the graphene electrode, so that the patterning customization of the graphene electrode can be realized.

[0070] S4, after the laser scanning is completed, the device to be processed is cooled at a preset cooling rate, the carbon source precursor is cut off in the uncarbonized area, and the patterned graphene electrode is obtained.

[0071] Specifically, the excess carbon source precursor can be cut off by using picosecond laser for “cold processing” cutting.

[0072] In the embodiments of the present application, the entire processing process of preparing the graphene electrode is carried out in an inert gas atmosphere, and the inert gas includes but is not limited to argon, nitrogen and the like.

[0073] The multi-physical field regulation graphene electrode preparation device and method provided by the embodiments of the present application can be used for preparing graphene electrodes for various flexible substrate devices or rigid substrate devices, especially suitable for preparing graphene electrodes for array devices, and can improve the production efficiency and large-scale capacity of the array devices.

[0074] Array device refers to a device composed of multiple same or similar functional units arranged in a certain rule, and the array device includes but is not limited to a sensor array, a light source and a photoelectric array, an electrode array, an antenna and a radio frequency array, a micro-electro-mechanical system (MEMS) array, a display and an imaging array, and the material of the array device includes but is not limited to a piezoelectric material, a semiconductor material, a metal material and an organic material.

[0075] Based on the above embodiments, in order to more specifically illustrate the implementation manner and beneficial effects of the technical scheme of the present application, the present application further provides the following specific embodiments, and it should be noted that the following specific embodiments are only exemplary in nature and do not limit the protection scope of the present application in any form.

[0076] Embodiment 1

[0077] In this embodiment, the multi-physical field regulation graphene electrode preparation device and method provided in the above embodiments are used to prepare a graphene electrode for an array device, and the graphene electrode is prepared by referring to Figure 4 、 5 , and the preparation of the graphene electrode includes the following steps:

[0078] Step 1, preparing an array device sample.

[0079] As shown in Figure 4 (a), a suitable device array material (for example, PZT piezoelectric ceramic) is selected, and the device material is subjected to surface cleaning and polishing treatment to improve the surface quality; then, the device material is cut into 10*10 mm array elements, the cut device array 100 is arranged in 3*3 array elements, and the spacing between the array elements is 5 mm; finally, the arranged device array 100 is transferred to a glass substrate 8 by using a thermal release tape.

[0080] The thermal release tape is preferably a low-residue tape, and the adhesion thereof can be reversibly released by applying external stimulation (heating, ultraviolet irradiation or chemical treatment, etc.), so as to avoid the pollution of the array element surface.

[0081] Step 2, coating a carbon source precursor.

[0082] Polyimide (PI) is dissolved in a solvent to prepare a solution with a concentration of 5-10 wt%, and a polyimide film with a thickness of 50 μm is cut into 50*50 mm as a carbon source precursor. Polyimide solution is spin-coated on the film as an adhesive, and then the arranged array device in step 1 is pressed on the carbon source precursor. The above sample is placed in an oven, and after baking at 60°C for 1 hour, a structure as shown in Figure 4 (b) is obtained, that is, the array device surface is covered with a layer of carbon source precursor 200.

[0083] Step 3, preparation of laser-induced graphene.

[0084] Place the array device coated with carbon source precursor on the processing platform of the multi-physical field regulated graphene electrode preparation device.

[0085] The 515nm picosecond laser is used, the defocusing amount is 5-8mm, the laser frequency is 200-400kHz, the laser pulse width is 2-8ps, the scanning speed is 100-400mm / s, and the laser power is 1W-4W.

[0086] The surface of the temperature field device (the bottom of the array device substrate) is set to 300-350℃, and the cooling rate after the processing is completed is 2-5℃ / min.

[0087] The electric field generating device is set to generate a vertical pulse electric field with a pulse width of 1-5ps, a frequency of 200-400kHz, and an electric field strength of 50-200V / cm between the upper and lower electrode plates.

[0088] The magnetic field generating device is set to generate a uniform magnetic field with a strength of 0.8-1.2T.

[0089] The ultrasonic generating device is set to generate ultrasonic waves with a frequency of 20-40kHz and a power of 80-150W, so that the temperature uniformity of the polyimide during the pyrolysis process is controlled within a difference range of ±5℃.

[0090] As shown in Figure 4 (c), set the laser scanning path, start each module of the multi-physical field regulated graphene electrode preparation device, and prepare a patterned graphene electrode 300 on the array device.

[0091] Step 4, post-processing of the graphene electrode.

[0092] Referring to Figure 5 , the prepared graphene electrode is post-processed, and the excess carbon source precursor is cut off by picosecond laser "cold processing" to obtain an array device as shown in Figure 4 (d).

[0093] If the graphene electrode on the reverse side of the array device is to be prepared, steps 1-4 can be repeated.

[0094] Step 5, packaging.

[0095] The prepared graphene electrode is packaged (the packaging material can be selected from polyimide, polydimethylsiloxane, epoxy resin, etc.) to protect the graphene electrode from the external environment.

[0096] The Raman spectrum characterization result of the graphene electrode prepared in this embodiment is shown in Figure 6 , the D, G, and 2D characteristic peaks indicate the successful preparation of the graphene structure; the SEM image of the graphene electrode is shown in Figure 7As shown, it can be seen that the graphene sheet layer structure has a large number of three-dimensional through pores, and has a high specific surface area.

[0097] From the above examples, it can be seen that the multi-physical field regulated graphene electrode preparation device and method provided by the application is based on laser-induced graphene technology, and the quality and performance of the graphene electrode are improved through multi-physical field regulation. The principle of achieving the beneficial effect through multi-physical field regulation is as follows:

[0098] First, the temperature field device generates a gradient temperature field in the thickness direction of the carbon source precursor, drives the carbon source molecular chain to migrate from the bottom interface of the carbon source precursor cover layer to the surface subjected to laser action, effectively supplements the carbon atom source of the laser processing area, avoids uneven supply of the carbon source, reduces vacancy structure defects and edge structure defects, and at the same time, the temperature field device can also control the cooling rate of the device to be processed, reducing the risk of cracking of the graphene electrode due to thermal stress;

[0099] Second, the orthogonal magnetic field and electric field constrain the horizontal diffusion of carbon atom plasma, reduce the diffusion radius of carbon atom plasma, realize precise control of the number of graphene layers, and improve the uniformity of the graphene electrode; at the same time, the electromagnetic field constrains the high-energy plasma in a small area controlled accurately, enhances the energy localization, and optimizes the energy utilization rate;

[0100] Third, the ultrasonic generating device generates micro-jets through ultrasonic cavitation effect, which can break the local steep temperature gradient of carbon source pyrolysis, improve the uniformity of graphene growth; at the same time, ultrasonic vibration can reduce the van der Waals force between graphene layers, form three-dimensional interconnected pores in the graphene electrode, and increase the specific surface area of the graphene electrode;

[0101] Fourth, the electric field generating device applies a force to the polar group in the carbon source precursor through the vertical pulsed electric field, drives the vertical migration of carbon atoms, suppresses the horizontal diffusion of carbon atoms, promotes the vertical stacking of graphene layers, improves the bonding force between the graphene electrode and the device to be processed, and reduces the contact resistance.

[0102] In addition, the traditional graphene electrode adopts a "growth-transferring" process, but the transferring process of the graphene electrode is easy to introduce residual glue and impurity pollution, and the operation of mechanical peeling or chemical etching is easy to cause damage and wrinkles of the graphene, thereby causing the interface resistance between the graphene electrode and the substrate to increase, and the stability and reliability of the device to decrease; the technical scheme provided by the embodiment of the application can prepare the graphene electrode in situ on the device, avoid the problems of graphene defects, pollution and damage caused by the peeling, cleaning, transferring and other steps in the traditional process, and greatly improve the reliability of the device.

[0103] For electrode preparation of array devices, conventional array devices need to process discrete array elements one by one, and need to go through complex array element positioning, alignment and fixing steps, and cannot realize synchronous processing of multiple array elements, and the array element spacing is difficult to accurately control (especially for micro sensor array), resulting in long production cycle, high cost, and difficult to adapt to large-scale manufacturing requirements. The technical scheme of laser-induced preparation of graphene electrode provided in the embodiments of the present application combines with the heat release adhesive tape assisted array element arrangement technology, can realize the accurate control of the array element spacing of 0.1 μm-10 mm, replace the complex process of processing array elements one by one, 3*3 and more array elements can be arranged and fixed synchronously, the production cycle is shortened, and the large-scale manufacturing requirements are met.

[0104] The above-described embodiments are only used to illustrate the technical solutions of the present application, rather than limit them; although the present application has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that they can modify the technical solutions recorded in the foregoing embodiments, or make equivalent replacement for part of the technical features; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present application.

Claims

1. A multi-physical field regulated graphene electrode preparation device, characterized in that, The device comprises a base, a laser generating device, a temperature field device, an ultrasonic generating device, an electric field generating device and a magnetic field generating device; The laser generating device is used for generating a laser beam; The temperature field device is arranged on the base and is used for generating a temperature gradient gradually decreasing upwards from the upper surface of the temperature field device; The electric field generating device comprises an upper electrode plate and a lower electrode plate, the lower electrode plate is arranged on the upper surface of the temperature field device, and the upper electrode plate is arranged above the lower electrode plate in parallel, and the electric field generating device is used for generating a vertical direction pulse electric field between the upper electrode plate and the lower electrode plate; The pulse electric field is synchronous with the frequency of the laser beam; The magnetic field generating device is arranged on the side surface of the temperature field device and is used for generating a magnetic field orthogonal to the vertical direction pulse electric field; The ultrasonic generating device is used for generating ultrasonic waves synchronous with the moving path of the laser beam.

2. A method for preparing a multi-physical-field regulated graphene electrode, using the multi-physical-field regulated graphene electrode preparation device of claim 1, characterized in that, The device comprises the following steps: S1, covering a carbon source precursor on the surface of a device to be processed, wherein the carbon source precursor is a polymer containing a polar group; S2, setting the laser parameters of the laser generating device, and setting the processing parameters of the temperature field device, the ultrasonic generating device, the electric field generating device and the magnetic field generating device; S3, placing the device to be processed covered with the carbon source precursor on the lower electrode plate of the electric field generating device, starting the laser generating device, the temperature field device, the ultrasonic generating device, the electric field generating device and the magnetic field generating device, and making the laser beam emitted by the laser generating device irradiate on the carbon source precursor according to a preset scanning path; S4, after the laser scanning is completed, cooling the device to be processed at a preset cooling rate, and removing the uncarbonized area of the carbon source precursor by laser to obtain a patterned graphene electrode.

3. The method of claim 2, wherein the method further comprises: The carbon source precursor is a polyimide.

4. The method of claim 2, wherein the method further comprises: The laser parameters comprise: outputting a picosecond laser, a defocusing amount of 5-8 mm, a laser frequency of 200 kHz-400 kHz, a laser pulse width of 2-8 ps, a laser scanning speed of 100-400 mm / s, and a laser power of 1-4 W.

5. The method of claim 4, wherein the method further comprises: The processing parameters of the electric field generating device comprise: outputting a pulse electric field, a pulse width of the pulse electric field of 1-5 ps, a frequency of 200 kHz-400 kHz, and an intensity of 50-200 V / cm.

6. The method of claim 2, wherein the method further comprises: The processing parameters of the magnetic field generating device comprise: a magnetic field intensity of 0.8-1.2 T in the area where the device to be processed is located.

7. The method of claim 2, wherein the method further comprises: The ultrasonic waves generated by the ultrasonic generating device have a frequency of 20 kHz-40 kHz and a power of 80-150 W. 8.The method for preparing a multi-physics field regulated graphene electrode according to claim 2, wherein, The processing parameters of the temperature field device comprise: an upper surface temperature of the temperature field device of 300-350 ℃, and a preset cooling rate of 2-5 ℃ / min.

9. A graphene electrode, characterized by, The graphene electrode is prepared by the multi-physical field regulated graphene electrode preparation device of claim 1 or by the multi-physical field regulated graphene electrode preparation method of any one of claims 2-8.

10. An array device comprising a substrate and a plurality of array elements disposed on the substrate, wherein, The array element is connected with a graphene electrode; The graphene electrode is prepared by the multi-physical field regulated graphene electrode preparation device of claim 1 or by the multi-physical field regulated graphene electrode preparation method of any one of claims 2-8.

Images