A nanotwinned copper-graphene composite patch antenna and a preparation method thereof

Abstract

The application discloses a nano-twin copper-graphene composite patch antenna and a preparation method thereof, and relates to the field of micro electro mechanical devices. The nano-twin copper-graphene composite patch antenna comprises a nano-twin copper-graphene composite antenna, a dielectric substrate and a protective layer covering the nano-twin copper-graphene composite antenna. The nano-twin copper-graphene composite antenna comprises copper and graphene, and the organizational structure of the nano-twin copper-graphene composite antenna comprises a twin structure. The nano-twin copper-graphene composite antenna doped with graphene improves the frequency band responsiveness and stability of the nano-twin copper-graphene composite patch antenna at different temperatures.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of micro-electro-mechanical devices, in particular to a nano-twin copper-graphene composite material patch antenna and a preparation method thereof. BACKGROUND

[0002] The world today is a world of rapid development of informatization, and 5G technology, Internet of Things (IoT) technology, etc. are developing vigorously. Mobile communication devices are increasingly evolving towards wearable and portable directions, which puts forward higher requirements for flexible, ultra-thin and highly integrated wireless communication elements. There is an extremely strong demand for flexible and ultra-thin wireless communication elements in fields such as life health monitoring and portable radio frequency tags. How to manufacture wireless communication elements that can meet the needs of flexibility and ultra-thinness while ensuring good radiation performance of the elements is a problem with extremely broad research prospects. The field of microstrip patch antennas has been thoroughly researched. Traditional high-performance microstrip patch antennas are designed based on traditional high-conductivity metals (such as copper, silver, gold, aluminum, etc.), and have been widely used in fields such as satellite communication, remote sensing detection, mobile devices, etc.

[0003] Microstrip patch antennas with high shape complexity often use printing and other methods for production due to their fine structure, and the processing procedure is complex, a large number of equipment are needed, and the manufacturing cost is high. However, for integrated microstrip radio frequency devices or conformal microstrip antennas with high shape complexity, the application of metal materials will be severely limited by their low flexibility and complex manufacturing process. Moreover, when the microstrip patch antenna is applied, the device generates heat, which leads to poor frequency band responsiveness and stability of the patch antenna at high temperatures. SUMMARY

[0004] In view of the deficiencies of the above related technologies, the application provides a nano-twin copper-graphene composite material patch antenna and a preparation method thereof. The nano-twin copper-graphene composite material antenna doped with graphene and nano-twin copper improves the frequency band responsiveness and stability of the nano-twin copper-graphene composite material patch antenna at different temperatures.

[0005] In a first aspect, the application provides a nano-twin copper-graphene composite material patch antenna using the following technical solution:

[0006] A nano-twin copper-graphene composite material patch antenna includes a nano-twin copper-graphene composite material antenna, a dielectric substrate, and a protective layer covering the nano-twin copper-graphene composite material antenna, the nano-twin copper-graphene composite material antenna includes copper and graphene, and the organizational structure of the nano-twin copper-graphene composite material antenna includes a twin structure.

[0007] Preferably, the graphene in the nanotwinned copper-graphene composite antenna is distributed in at least one of the twinning boundary region, the grain boundary region and the non-coherent twinning boundary region.

[0008] Preferably, the twinning spacing of the twinned structure is 10-500 nm.

[0009] Preferably, the nanotwinned copper-graphene composite antenna has a width dimension of 100-800 μm and a thickness dimension of 1-100 μm.

[0010] Preferably, the dielectric substrate has a dielectric constant of 3-6 and a thickness of 0.5-2 mm.

[0011] Preferably, the dielectric substrate comprises one or more of polyethylene terephthalate, polydimethylsiloxane and epoxy glass fiber composite. Preferably, 1 mm thick polytetrafluoroethylene plate (dielectric constant 2) is used as the dielectric substrate in consideration of economy, practicability and thermal stability at high frequency.

[0012] Preferably, 1 mm thick polytetrafluoroethylene plate (dielectric constant 2) is used as the dielectric substrate in consideration of economy, practicability and thermal stability at high frequency.

[0013] In a second aspect, the application provides a preparation method of a nanotwinned copper-graphene composite patch antenna, which adopts the following technical scheme:

[0014] The preparation method of the nanotwinned copper-graphene composite patch antenna comprises the following steps: placing a copper anode and a cathode plate in an electroplating solution containing copper sulfate and graphene, constructing an electrolyte channel between the cathode plate and the anode, applying a pulse current through the anode and the cathode plate and moving the anode relative to the cathode plate to perform electrodeposition on the cathode plate, and obtaining the nanotwinned copper-graphene composite antenna.

[0015] After the nanotwinned copper-graphene composite antenna is taken off from the cathode plate, cleaned and fixed on a dielectric substrate, a protective layer covering the antenna is fixed on the dielectric substrate, and the nanotwinned copper-graphene composite patch antenna is obtained.

[0016] Preferably, the electroplating solution comprises copper sulfate, polyethylene glycol, graphene and sodium chloride, the concentration of the copper sulfate is 100-150 g / L, the concentration of the polyethylene glycol is 0.03-0.08 g / L, the concentration of the graphene is 0.001-0.15 g / L, and the concentration of the sodium chloride is 50-100 mg / L.

[0017] Preferably, the electroplating solution comprises copper sulfate, polyethylene glycol, graphene and sodium chloride, the concentration of the copper sulfate is 128 g / L, the concentration of the polyethylene glycol is 0.05 g / L, the concentration of the graphene is 0.01 g / L, and the concentration of the sodium chloride is 80 mg / L.

[0018] Preferably, the electroplating solution further comprises 2-mercaptobenzimidazole with a concentration of 0.0003-0.0008 g / L, 1-2 ethylene thiourea with a concentration of 0.0003-0.0008 g / L, and sodium polydithiobis propane sulfonate with a concentration of 0.008-0.012 g / L.

[0019] Preferably, the electroplating solution further comprises 2-mercaptobenzimidazole with a concentration of 0.0005 g / L, 1-2 ethylene thiourea with a concentration of 0.0005 g / L, and sodium polydithiobis propane sulfonate with a concentration of 0.01 g / L.

[0020] Preferably, the electrolyte further comprises an oxidizing agent, the oxidizing agent is hydrogen peroxide with a weight percentage of 27.5-35%, and the addition amount is 1-10 mL / L.

[0021] Preferably, the pH of the electroplating solution is not greater than 1.

[0022] Preferably, the pulse current has a voltage of 10-50 V, a current density of 300-500 mA / cm 2 , a conduction time of 10-50 ms, and a disconnection time of 200-300 ms.

[0023] In summary, the present application includes at least one of the following beneficial technical effects:

[0024] 1. The present application improves the frequency band responsiveness and stability of the nanotwinned copper-graphene composite patch antenna at different temperatures through the nanotwinned copper-graphene composite antenna doped with graphene.

[0025] 2. The present application improves the electrical conductivity and mechanical properties of the nanotwinned copper-graphene composite patch antenna by forming a graphene reinforced phase through the organizational structure of the nanotwinned copper-graphene composite patch antenna including a twin structure.

[0026] 3. The present application improves the frequency band responsiveness and stability of the nanotwinned copper-graphene composite patch antenna at different temperatures by preparing the nanotwinned copper-graphene composite antenna through pulse electrodeposition and making the nanotwinned copper-graphene composite antenna into a nanotwinned copper-graphene composite patch antenna, and still obtaining a twin structure in the case of doping graphene, and the overall organizational structure is stable and dense. BRIEF DESCRIPTION OF DRAWINGS

[0027] Figure 1 This is a physical image of the nanotwinned copper-graphene composite material antenna of Embodiment 1 of this application;

[0028] Figure 2 This is a transmission electron microscope image of the nanotwinned copper-graphene composite material antenna of Embodiment 1 of this application;

[0029] Figure 3 This is the S-type of the nanotwinned copper-graphene composite material patch antenna of Embodiment 1 of this application. 11 Performance graph;

[0030] Figure 4 The nanotwinned copper-graphene composite material patch antennas of Comparative Examples 1-2 and Example 1 of this application demonstrate S in the 2.7 GHz band. 11 Temperature stability test comparison chart. Detailed Implementation

[0031] The present application will be further described in detail below with reference to the embodiments. The following embodiments are for illustrative purposes only and should not be considered as limiting the scope of the invention. Unless otherwise specified, specific conditions in the following embodiments were performed under conventional conditions or conditions recommended by the manufacturer. Unless otherwise specified, the methods used are conventional methods known in the art, and the consumables and reagents used are commercially available. Unless otherwise stated, the technical and scientific terms used herein have the same meaning as those familiar to those skilled in the art. Furthermore, any methods or materials similar to or equivalent to those described herein may also be applied to the present invention.

[0032] The raw materials used in the examples and comparative examples are all commercially available.

[0033] Example 1

[0034] Example 1 of this application provides a nano-twinned copper-graphene composite material patch antenna, the preparation method of which is as follows: (1) Prepare a basic electroplating solution with copper sulfate concentration of 128 g / L, polyethylene glycol concentration of 0.05 g / L, graphene concentration of 0.1 g / L, sodium chloride concentration of 80 mg / L, 2-mercaptobenzimidazole concentration of 0.0005 g / L, 1-2-ethylidene thiourea concentration of 0.0005 g / L and sodium polydisulfide dipropane sulfonate concentration of 0.01 g / L, adjust the pH to 1 with sulfuric acid and use 120 W power ultrasonic waves with a frequency of 40 KHz to uniformly disperse the graphene, and add the electroplating solution to the plating tank.

[0035] (2) using copper metal as anode, stainless steel plate as cathode plate, installing anode in nozzle filled with electroplating solution, installing cathode plate in plating bath, building an electrolyte channel between cathode plate and anode by controlling electroplating solution in nozzle to flow into plating bath, applying pulse current through anode and cathode plate, voltage of pulse current: 40 V, current density: 400 mA / cm 2 , on time: 10 ms, off time: 40 ms, and making anode move in a snake shape relative to cathode plate to perform electrodeposition on cathode plate, obtaining a nanotwin copper-graphene composite material antenna in a snake shape with thickness: 30 μm and width: 500 μm, as shown in Figure 1

[0036] (3) taking nanotwin copper-graphene composite material antenna off cathode plate, washing with alcohol and water, then pasting on one side of dielectric substrate and pasting ground layer on the other side, covering nanotwin copper-graphene composite material antenna with polyimide tape and pasting on dielectric substrate to form a protective layer, obtaining the nanotwin copper-graphene composite material patch antenna (marked as Gr-ntCu), which is connected with antenna terminal in use by using conductive glue or welding.

[0037] Comparative Example 1

[0038] Comparative Example 1 provides a patch antenna, and the preparation method is as follows: (1) configuring a basic electroplating solution with copper sulfate concentration of 128 g / L, polyethylene glycol concentration of 0.05 g / L, graphene concentration of 0.1 g / L, sodium chloride concentration of 80 mg / L, 2-mercaptobenzimidazole concentration of 0.0005 g / L, 1-2 ethylene thiourea concentration of 0.0005 g / L, and polydithiodipropyl sulfonic acid sodium concentration of 0.01 g / L, adjusting pH to 1 with sulfuric acid, and uniformly dispersing graphene by using 120-watt ultrasonic wave with a frequency of 40 KHz to obtain electroplating solution and add into plating bath.

[0039] (2) using copper metal as anode, stainless steel plate as cathode plate, installing anode in nozzle filled with electroplating solution, installing cathode plate in plating bath, building an electrolyte channel between cathode plate and anode by controlling electroplating solution in nozzle to flow into plating bath, applying direct current voltage of 10 V and current density of 50 mA / cm 2 through anode and cathode plate, and making anode move in a snake shape relative to cathode plate to perform electrodeposition on cathode plate, obtaining a composite material patch antenna in a snake shape with thickness: 30 μm and width: 500 μm, as shown in Figure 1

[0040] ​​(3) The nano-twin copper-graphene composite material antenna is taken off from the cathode plate, washed with alcohol and water, then pasted on one side of the dielectric substrate and the ground layer is pasted on the other side, the nano-twin copper-graphene composite material antenna is covered with polyimide tape and pasted on the dielectric substrate to form a protective layer, and the nano-twin copper-graphene composite material patch antenna (labeled as DC-Cu) is obtained. When the nano-twin copper-graphene composite material patch antenna is used, it is connected with the antenna terminal by using conductive glue or welding.

[0041] Comparative Example 2

[0042] Comparative Example 2 provides a patch antenna, and the preparation method is as follows: coarse-grained copper wires are used to press-form using a mold to prepare a pure coarse-grained copper antenna with the same shape as that of Example 1, and the step (3) of Example 1 is used to prepare a coarse-grained copper patch antenna (labeled as coarse).

[0043] Test detection

[0044] (1) The nano-twin copper-graphene composite material antenna of Example 1 is imaged by transmission electron microscopy, as shown in Figure 2 .

[0045] (2) The S11 performance graph of the nano-twin copper-graphene composite material patch antenna of Example 1 is measured, as shown in Figure 3 , wherein the abscissa represents the signal frequency band, and the ordinate represents the frequency band loss.

[0046] (3) The S 11 temperature stability of the nano-twin copper-graphene composite material patch antennas of Comparative Examples 1-2 and Example 1 is tested at 2.7G frequency band, and the S 11 temperature stability comparison graph is shown in Figure 4 .

[0047] Result analysis

[0048] The following Figures 1-4 provides experimental results, and the present application is described in detail.

[0049] Referring to Figure 1 , the width of the nano-twin copper-graphene composite material antenna of Example 1 is about 700μm, and the width is uniform, the outline is clear, and the size is accurate, which shows that the method of preparing the nano-twin copper-graphene composite material patch antenna by configuring the electroplating solution and using electrodeposition is beneficial to improve the forming effect and size accuracy of the micron-level nano-twin copper-graphene composite material antenna.

[0050] Referring to Figure 2It can be known that the nano-twin copper-graphene composite patch antenna of the embodiment 1 of the application has a high-density twin structure in the organizational structure of the nano-twin copper-graphene composite patch antenna, the twin spacing thereof is 50-100 nm, and the graphene is densely distributed in the grain interior and at the grain boundary, the overall organizational structure is stable and dense, and there is no common heat processing defect such as a pore, which indicates that the preparation method of the nano-twin copper-graphene composite patch antenna of the application can successfully prepare the nano-twin copper-graphene composite patch antenna doped with graphene and containing a twin structure.

[0051] With reference to Figure 3 It can be known that the minimum frequency band loss of the nano-twin copper-graphene composite patch antenna of the embodiment 1 of the application corresponds to an abscissa of 3.0 GHz, that is, the nano-twin copper-graphene composite patch antenna of the embodiment 2 of the application has a better frequency band response at the frequency band of 3.0 GHz. In combination with Figure 4 It can be known that the nano-twin copper-graphene composite patch antenna of the embodiment 1 has a good temperature stability compared with the patch antennas of the comparative examples 1-2, has a better frequency band response and stability at different temperatures, and has a smaller signal loss at normal temperature, which indicates that the frequency band response and stability of the nano-twin copper-graphene composite patch antenna of the embodiment 1 at different temperatures are good.

[0052] The specific embodiment is only an explanation of the application, and is not a limitation of the application, and those skilled in the art can make a modification of the embodiment without a creative contribution according to the need after reading the specification, but as long as the modification is within the scope of the claims of the application, it is protected by the patent law.

Claims

1. A nanotwinned copper-graphene composite patch antenna, characterized by: The antenna includes a nanotwinned copper-graphene composite antenna, a dielectric substrate, and a protective layer covering the nanotwinned copper-graphene composite antenna, the nanotwinned copper-graphene composite antenna includes copper and graphene, and the nanotwinned copper-graphene composite antenna has a twinned structure; the graphene in the nanotwinned copper-graphene composite antenna is distributed in at least one of a twinned boundary region, a grain boundary region, and a non-coherent twinned boundary region; the twinned structure has a twinned spacing of 10-500 nm; the nanotwinned copper-graphene composite antenna has a width of 100-800 μm and a thickness of 1-100 μm.

2. The nanotwinned copper-graphene composite patch antenna of claim 1, wherein: The dielectric substrate has a dielectric constant of 2-6 and a thickness of 0.5-2 mm.

3. The nanotwinned copper-graphene composite patch antenna of claim 2, wherein: The dielectric substrate includes one or more of polyethylene terephthalate, polydimethylsiloxane, and an epoxy glass fiber composite.

4. A method for preparing a nanotwinned copper-graphene composite patch antenna according to any one of claims 1-3, characterized in that: The method includes the following steps: A copper anode and a cathode plate are placed in an electroplating solution containing copper sulfate and graphene, an electrolyte channel is formed between the cathode plate and the anode, a pulse current is applied through the anode and the cathode plate, and the anode is moved relative to the cathode plate to perform electrodeposition on the cathode plate, thereby obtaining a nanotwinned copper-graphene composite antenna; The nanotwinned copper-graphene composite antenna is removed from the cathode plate, cleaned, and then fixed to the dielectric substrate, and a protective layer covering the antenna is then fixed to the dielectric substrate, thereby obtaining the nanotwinned copper-graphene composite patch antenna.

5. The method for preparing a nanotwinned copper-graphene composite material patch antenna according to claim 4, characterized in that: The electroplating solution includes copper sulfate, polyethylene glycol, graphene, and sodium chloride, the concentration of the copper sulfate is 100-150 g / L, the concentration of the polyethylene glycol is 0.03-0.08 g / L, the concentration of the graphene is 0.001-0.15 g / L, and the concentration of the sodium chloride is 50-100 mg / L.

6. The method for preparing a nanotwinned copper-graphene composite material patch antenna according to claim 4, characterized in that: The electroplating solution further includes 2-mercaptobenzimidazole with a concentration of 0.0003-0.0008 g / L, 1-2 ethylene thiourea with a concentration of 0.0003-0.0008 g / L, and sodium polydithiobispropane sulfonate with a concentration of 0.008-0.012 g / L.

7. The method for preparing a nanotwinned copper-graphene composite material patch antenna according to claim 4, characterized in that: The pulse current has a voltage of 10-50 V, a current density of 300-500 mA / cm 2 , a conduction time of 10-50 ms, and an off time of 200-300 ms.

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