CN111048902A - Transparent antenna and preparation method thereof - Google Patents
Transparent antenna and preparation method thereof Download PDFInfo
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- CN111048902A CN111048902A CN201911337717.4A CN201911337717A CN111048902A CN 111048902 A CN111048902 A CN 111048902A CN 201911337717 A CN201911337717 A CN 201911337717A CN 111048902 A CN111048902 A CN 111048902A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/38—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/364—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
- H01Q1/36—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
- H01Q1/364—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor
- H01Q1/368—Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith using a particular conducting material, e.g. superconductor using carbon or carbon composite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01Q—ANTENNAS, i.e. RADIO AERIALS
- H01Q1/00—Details of, or arrangements associated with, antennas
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Abstract
The invention discloses a transparent antenna: the transparent antenna comprises a transparent dielectric layer and a transparent conducting layer on one surface of the dielectric layer, wherein the conducting layer comprises a graphene film and a metal nanowire network, and an antenna pattern is arranged on the conducting layer; or the transparent antenna comprises a transparent dielectric layer, a transparent conducting layer on one surface of the dielectric layer and a grounding layer on the other surface of the dielectric layer, wherein the conducting layer comprises a graphene film and a metal nanowire network. The invention also provides a preparation method of the transparent antenna. According to the invention, the excellent conductivity of the metal nanowires, the conductivity characteristic and high light transmittance of the graphene film are combined, the graphene film in the conductive layer is used as a connector to reduce the usage amount of the metal nanowires, and the light transmittance and the conductivity of the conductive film are improved; under the condition of meeting the requirement of specific light transmittance, the conductive performance of the conductive film is improved, so that the radiation efficiency of the transparent antenna is improved.
Description
Technical Field
The invention relates to the field of wireless communication application, in particular to a transparent antenna containing a graphene film and a metal nanowire and a preparation method thereof.
Background
An antenna is one of the most important components in a wireless communication system for transmitting and receiving electromagnetic waves. With the rapid development of the 5G wireless communication technology, the application scenarios are more and more abundant, so that the requirements for the antenna performance are more and more diversified. In order to provide good conformality, stealth and stability to an antenna for integration in a wireless communication system of a mobile terminal, a satellite, an automobile, etc., the antenna needs to have a light-transparent characteristic. On the other hand, with the development of intellectualization, miniaturization, and light weight of wearable electronic devices, the antenna also needs to have flexibility. Antennas that meet the above applications need to have high conductivity, high transparency, flexibility, and the like.
Common optical transparent conductors include Indium Tin Oxide (ITO), zinc oxide-based transparent conductive films, metal ultrathin films, networks composed of metal nanowires, graphene, and other materials. Light transmittance and electrical conductivity are key indicators to determine whether a material is suitable for use in the preparation of transparent antennas. Although the antenna manufactured by using the ITO and zinc oxide based transparent conductive film has high light transmittance and conductivity, the ITO and zinc oxide based transparent conductive film is lack of flexibility, scarce in raw material resources and expensive in cost. The metal thin film has excellent conductive characteristics but poor light transmittance. The conductivity of the network consisting of the metal nanowires is determined by the network consisting of the metal nanowires, and the higher the density of the metal nanowires in the network is, the better the conductivity is; the light transmittance is determined by the size of the randomly formed mesh, and the size of the mesh is also related to the density of the metal nanowires in the network, and the higher the density of the metal nanowires, the smaller the average size of the mesh is, and the poorer the light transmittance is. Thus, the optical transparency and electrical conductivity are inversely related for the network of metal nanowires. The metal nano-wire can be formed into a film by adopting a printing technology, and the conductive film has good flexibility.
Graphene has high light transmittance, high chemical stability and excellent mechanical flexibility, but the graphene film prepared by the chemical vapor deposition method at present is basically a polycrystalline graphene material formed by splicing small-crystal-domain graphene crystals, so that the conductivity is influenced by the defects of crystal boundaries and the like. The conductivity of the antenna material is an important factor for determining the radiation performance of the antenna. Generally, the sheet resistance of the graphene (monolayer) prepared at present is generally in
Above, cannot satisfyPerformance requirements of transparent antennas.
Therefore, a new transparent conductive material or a composite structure of several transparent conductive materials is needed to be found to meet the performance requirements in the field of transparent antennas.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a transparent antenna and a preparation method thereof, aiming at solving the problems of low light transmittance, poor electric conductivity and the like of the conventional transparent antenna.
The invention provides a transparent antenna, which comprises a transparent dielectric layer and a transparent conducting layer (transparent conducting layer) on one surface of the dielectric layer, wherein the conducting layer comprises a graphene film and a metal nanowire network (namely, a composite structure formed by the graphene film and the metal nanowire network), and an antenna pattern is arranged on the conducting layer. Namely, the transparent antenna has a structure of a dielectric layer/graphene film/metal nanowire network, or a dielectric layer/metal nanowire network/graphene film.
The invention also provides a transparent antenna, which comprises a transparent dielectric layer, a transparent conducting layer on one surface of the dielectric layer and a grounding layer on the other surface of the dielectric layer, wherein the conducting layer comprises a graphene film and a metal nanowire network (namely, a composite structure formed by the graphene film and the metal nanowire network). That is, the transparent antenna has a structure of a ground layer/a dielectric layer/a graphene film/a metal nanowire network, or a ground layer/a dielectric layer/a metal nanowire network/a graphene film.
In the transparent antenna described above:
the material of the dielectric layer includes but is not limited to transparent dielectric materials such as transparent glass, quartz, polyethylene terephthalate (PET), Polyimide (PI), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), parylene or hexagonal boron nitride (h-BN).
The graphene film is composed of 1-6 layers of graphene. Preferably, the graphene film is composed of 1-2 layers of graphene.
The metal nanowire comprises but is not limited to a silver nanowire, a copper nanowire or an aluminum nanowire, and the diameter of the metal nanowire is 5-100 nm. Preferably, the diameter of the metal nanowire is 10-40nm, and the length of the metal nanowire is in a nanometer to millimeter level.
The metal nanowires in the metal nanowire network account for 10-65% of the area of the antenna pattern, the metal nanowires are distributed uniformly, and correspondingly, the meshes account for 90-35%.
The graphene film is prepared by a chemical vapor deposition method which is commonly used at present, and can be prepared by other technical methods along with the progress of the preparation technology. The graphene film can be transferred to a dielectric layer or a metal nano network after being prepared; preferably, the graphene thin film is grown directly on the dielectric layer or on the metal nano-network.
The metal nanowire network is formed by printing a metal nanowire solution on a dielectric layer or a graphene film by a printing method.
For the metal nanowire network, the conductivity is determined by the network composed of the metal nanowires, and the light transmittance is determined by the meshes; the larger the proportion of the meshes in the whole film is, the higher the light transmittance is, but the poorer the conductivity is; conversely, because of the excellent conductivity of metals, the smaller the proportion of the mesh to the entire film, the better the conductivity but the lower the light transmittance. The prepared graphene film/metal nanowire network or metal nanowire network/graphene film composite structure can meet the light transmittance requirement and has high conductivity; the graphene film is beneficial to forming more effective conductive paths in the metal nanowire network, and has a protection effect on the metal nanowires and the like.
The invention also provides a preparation method of the transparent antenna, the structure of the transparent antenna is a dielectric layer/graphene film/metal nanowire network or a dielectric layer/metal nanowire network/graphene film, and the preparation method comprises the following steps:
(1) pretreating the dielectric layer;
(2) preparing a transparent conductive layer on the surface of the dielectric layer;
(3) and forming the designed antenna pattern on the transparent conductive layer by a micro-nano processing technology.
In the step (1), the method for pretreating the dielectric layer mainly comprises organic solvent cleaning, plasma treatment and the like.
In the step (2), according to the material of the dielectric layer and the characteristics of the metal nanowire, the graphene film can be directly grown on the dielectric layer or the metal nano network by adopting a chemical vapor deposition method; the graphene film prepared by the chemical vapor deposition method can also be transferred to a dielectric layer or a metal nanowire network.
In the step (2), the metal nanowire network is prepared by printing the metal nanowire solution on the dielectric layer or the graphene film layer. Printing methods include, but are not limited to, spin coating, doctor blading, screen printing, and the like. The light transmittance and the area resistance of the metal nanowire network can be adjusted by adjusting the printing process parameters, such as the printing speed and the printing times, and the concentration of the metal nanowire solution.
In the step (3), the micro-nano processing technology includes, but is not limited to, photolithography, electron beam etching, laser engraving, or the like.
In step (3), the antenna pattern is designed according to a usage scenario.
The transparent antenna also comprises a feed structure.
Optionally, a transparent protective layer is prepared on the transparent conductive layer to protect the whole antenna.
And by adopting the flexible dielectric layer and the flexible conductive layer, the flexible transparent antenna can be manufactured.
The invention also provides another preparation method of the transparent antenna, the structure of the antenna is a grounding layer/a dielectric layer/a graphene film/a metal nanowire network, or the grounding layer/the dielectric layer/the metal nanowire network/the graphene film, and the preparation method comprises the following steps:
(1) pretreating the dielectric layer;
(2) preparing a grounding layer on one surface of the dielectric layer;
(3) preparing a transparent conducting layer on the other surface of the dielectric layer;
(4) and forming the designed antenna pattern on the transparent conductive layer by a micro-nano processing technology.
In the step (1), the method for pretreating the dielectric layer mainly comprises organic solvent cleaning, plasma treatment and the like.
In the step (2), the structure of the transparent conductive layer is a graphene film/metal nanowire network or a composite structure of a metal nanowire network/graphene film. According to the material of the dielectric layer and the characteristics of the metal nanowire, the graphene film can be directly grown on the dielectric layer or the metal nano network by adopting a chemical vapor deposition method; the graphene film prepared by the chemical vapor deposition method can also be transferred to a dielectric layer or a metal nanowire network.
In the step (2), the metal nanowire network is prepared by printing the metal nanowire solution on the dielectric layer or the graphene film layer. Printing methods include, but are not limited to, spin coating, doctor blading, screen printing, and the like. The light transmittance and the area resistance of the metal nanowire network can be adjusted by adjusting the printing process parameters, such as the printing speed and the printing times, and the concentration of the metal nanowire solution.
In the step (3), the micro-nano processing technology includes, but is not limited to, photolithography, electron beam etching, laser engraving, or the like.
In step (3), the antenna pattern is designed according to a usage scenario.
The grounding layer is a conductor and has excellent light transmission. The preparation method can be selected according to different material characteristics, and the conductor materials include but are not limited to ITO, metal thin layers, graphene films, metal nanowires, conductive polymer PEDOT: PSS (poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate) and the like.
Optionally, a transparent protective layer is prepared on the transparent conductive layer to protect the whole antenna.
By adopting the flexible dielectric layer, the conductive layer and the grounding layer, the flexible transparent antenna can be manufactured.
Compared with the prior art, the invention has the main advantages that: the invention utilizes the excellent conductive performance of the metal nanowires, the conductive characteristic of the graphene film and the high light transmittance of the graphene film. The metal film or the metal nanowire has poor light transmittance, and the graphene film is used as the connecting body, so that the using amount of the metal nanowire can be reduced, and the light transmittance and the conductivity of the transparent conductive film can be improved. The invention improves the conductivity of the conductive film under the condition of meeting the requirement of specific light transmittance, thereby improving the radiation efficiency of the transparent antenna. And combining the advantages of the graphene film and the metal nanowires to form the transparent conducting layer consisting of the graphene film and the metal nanowire network. Meanwhile, the graphene film and the metal nanowire have the bending property, so that a flexible transparent antenna can be prepared; the graphene film has the characteristic of impermeability to molecules and atoms, so that the stability of the composite structure transparent conductive film can be improved; the metal nano-wire can be formed into a film by adopting a printing method, so that the preparation cost can be reduced.
Drawings
Fig. 1 is a schematic structural diagram of a transparent antenna provided in the present invention;
fig. 2 is a scanning electron micrograph of the silver nanowires/graphene prepared in example 1 (graphene is difficult to observe here due to its transparency);
fig. 3 is a characteristic diagram of light transmittance and sheet resistance of a transparent conductive layer of a silver nanowire, silver nanowire/graphene film composite structure;
fig. 4 is a schematic flow chart of the preparation of the transparent antenna of example 2;
fig. 5 is a schematic flow chart of the preparation of the transparent antenna of example 3;
wherein: 1-dielectric layer, 2-conductive layer, 3-ground layer, 4-antenna pattern, 5-antenna pattern.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out under conventional conditions or conditions recommended by the manufacturers.
The schematic structural diagram of the transparent antenna provided by the invention is shown in (a) in fig. 1 and (b) in fig. 1:
as shown in fig. 1 (a), the transparent antenna provided by the present invention includes a transparent dielectric layer and a transparent conductive layer on a surface of the dielectric layer, wherein the conductive layer is a structure formed by compositing a metal nanowire network and a graphene film. That is, the structure of the transparent antenna may be a dielectric layer/a graphene film/a metal nanowire network, or a dielectric layer/a metal nanowire network/a graphene film.
As shown in fig. 1 (b), another transparent antenna provided by the present invention includes a transparent dielectric layer, a transparent conductive layer on the dielectric layer, and a ground layer on the other surface of the dielectric layer, wherein the conductive layer is a structure formed by compounding a metal nanowire network and a graphene film. That is, the transparent antenna may have a structure of a ground layer/a dielectric layer/a graphene film/a metal nanowire network, or a ground layer/a dielectric layer/a metal nanowire network/a graphene film.
The dielectric layer includes, but is not limited to, transparent dielectric materials such as transparent glass, quartz, polyethylene terephthalate (PET), Polyimide (PI), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), parylene, or hexagonal boron nitride (h-BN). The graphene thin film is composed of 1-6 layers of graphene, preferably 1-2 layers of graphene. The metal nanowires are silver, copper or aluminum nanowires, and the diameter of the metal nanowires is 5-100nm, preferably 10-40 nm.
EXAMPLE 1 preparation of transparent antenna conductive layer
The embodiment provides a preparation method of a transparent antenna conducting layer, which comprises the following basic steps:
respectively carrying out ultrasonic cleaning on the glass sheet for 10 minutes by using acetone, ethanol and deionized water in sequence, and then blowing the glass sheet by using nitrogen; spin-coating the silver nanowire with the concentration of 0.1-5mg/mL on the cleaned glass sheet by using a spin-coating instrument, wherein the spin-coating speed is 1000-; and transferring the graphene film to a network formed by silver nanowires by using a conventional method for transferring graphene by taking PMMA (polymethyl methacrylate) as a supporting layer, so as to form a structure of a glass sheet/silver nanowire network/graphene film. The glass sheet is a dielectric layer, and the silver nanowire network/graphene film is a conductive layer. Fig. 2 is a scanning electron mirror image of the transparent conductive layer of the prepared glass/silver nanowire network/graphene thin film (note: graphene is difficult to observe here due to its high transparency).
The proportion (10-65%) of the metal nanowires in the metal nanowire network to the area of the antenna pattern can be adjusted by adjusting the spin coating rotation speed, the spin coating time, the spin coating times and the concentration of the metal nanowires (such as silver, copper, aluminum and the like), and the area resistance and the light transmittance are optimized.
The graphene film layer can also be prepared on a dielectric layer such as glass, quartz and the like, and then the metal nanowire is printed on the graphene film to form the conductive layer of the transparent antenna. The graphene film can be prepared by growing on the surface of a medium layer such as glass, quartz and the like by adopting a chemical vapor deposition method; the graphene film grown in advance can also be transferred to the surface of a dielectric layer such as glass, quartz and the like. At this time, the structure of the prepared transparent antenna is a dielectric layer/graphene film/metal nanowire network.
For nanowires such as copper, in addition to using a transfer technique, a chemical vapor deposition method may also be used to grow a graphene film on the metal nanowires.
The metal nanowire network is prepared by printing a metal nanowire solution on a dielectric layer or a graphene film layer. Printing methods include, but are not limited to, spin coating, doctor blading, screen printing, and the like. The light transmittance and the area resistance of the metal nanowire network can be adjusted by adjusting the printing process parameters, such as the printing speed, the printing times and the like, and the concentration of the metal nanowire solution.
Alternatively, a transparent protective layer, such as PMMA for transferring the graphene film (in this case, PMMA is not removed after transferring the graphene film), is prepared on the transparent conductive layer for protecting the entire antenna.
Fig. 3 is a characteristic diagram of Transmittance and Sheet resistance of a transparent conductive film with a composite structure of silver nanowires and silver nanowire/graphene films (Sheet resistance in abscissa is Sheet resistance, and Transmittance at 500nm in ordinate is Transmittance at 500 nm), and it can be seen that the Sheet resistance is different under different transmittances; meanwhile, the performance of the silver nanowire/graphene composite structure transparent conductive film is superior to that of a silver nanowire alone. The diameter of the silver nanowire is 20nm, the graphene film is single-layer graphene, and the metal nanowire accounts for 10-65% of the area of the antenna pattern.
EXAMPLE 2 preparation of transparent antenna
As shown in fig. 4, the method for manufacturing a transparent antenna provided in this embodiment includes the following basic steps:
(1) pretreating the dielectric layer, namely removing pollutants on the surface of the dielectric layer and changing the surface characteristics such as increasing the hydrophilicity by adopting methods such as organic solvent cleaning, plasma treatment and the like;
(2) a transparent conductive layer was prepared as in example 1;
(3) forming a designed antenna pattern on the transparent conducting layer by a micro-nano processing technology, wherein the micro-nano processing technology comprises but is not limited to photoetching, electron beam etching or laser engraving and the like; the antenna pattern is designed according to the usage scenario.
EXAMPLE 3 preparation of transparent antenna
As shown in fig. 5, the method for manufacturing a transparent antenna provided in this embodiment includes the following basic steps:
(1) pretreating the dielectric layer, namely removing pollutants on the surface of the dielectric layer and changing the surface characteristics such as increasing the hydrophilicity by adopting methods such as organic solvent cleaning, plasma treatment and the like;
(2) preparing a grounding layer on one surface of the preprocessed dielectric layer, wherein the grounding layer has the conductive capability and high transparency;
(3) a transparent conductive layer was prepared as in example 1;
(4) forming a designed antenna pattern on the transparent conducting layer by a micro-nano processing technology, wherein the micro-nano processing technology comprises but is not limited to photoetching, electron beam etching or laser engraving and the like; the antenna pattern is designed according to the usage scenario.
The grounding layer is a conductor and has excellent light transmission, and if a flexible transparent antenna is manufactured, the grounding layer is required to have flexibility; the preparation method can be selected according to different material characteristics, and the conductor materials include but are not limited to ITO, metal thin layers, graphene films, metal nanowires, conductive polymer PEDOT: PSS (poly 3, 4-ethylenedioxythiophene: polystyrene sulfonate) and the like.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. The transparent antenna is characterized by comprising a transparent dielectric layer and a transparent conducting layer on one surface of the dielectric layer, wherein the conducting layer comprises a graphene film and a metal nanowire network, and an antenna pattern is arranged on the conducting layer.
2. The transparent antenna of claim 1, wherein the transparent antenna comprises a transparent dielectric layer, a transparent conductive layer on one surface of the dielectric layer, and a ground layer on the other surface of the dielectric layer, the conductive layer comprising a graphene film and a metal nanowire network.
3. The transparent antenna of claim 1 or 2, wherein the dielectric layer is made of a material selected from transparent glass, quartz, polyethylene terephthalate, polyimide, polyethylene naphthalate, polymethyl methacrylate, parylene or hexagonal boron nitride.
4. The transparent antenna of claim 1 or 2, wherein the graphene film is formed from 1-6 layers of graphene.
5. The transparent antenna as claimed in claim 1 or 2, wherein the metal nanowires are selected from silver nanowires, copper nanowires or aluminum nanowires, and the diameter of the metal nanowires is 5-100 nm.
6. The transparent antenna of claim 1 or 2, wherein the metal nanowires in the metal nanowire network occupy 10-65% of the area of the antenna pattern.
7. A method for preparing a transparent antenna as claimed in any one of claims 1 and 3 to 6, characterized in that it comprises the following steps:
(1) pretreating the dielectric layer;
(2) preparing a transparent conducting layer on the surface of the dielectric layer;
(3) and forming the designed antenna pattern on the transparent conductive layer by a micro-nano processing technology.
8. The method for manufacturing a transparent antenna according to claim 7, wherein in the step (2), the graphene film prepared in advance is transferred onto the dielectric layer or the metal nano network, or the graphene film is directly grown on the dielectric layer or the metal nano network; and printing the metal nanowire solution on the dielectric layer or the graphene film by adopting a printing method for the metal nanowire network.
9. A method for preparing a transparent antenna as claimed in any one of claims 2 and 3 to 6, characterized in that it comprises the following steps:
(1) pretreating the dielectric layer;
(2) preparing a grounding layer on one surface of the dielectric layer;
(3) preparing a transparent conducting layer on the other surface of the dielectric layer;
(4) and forming the designed antenna pattern on the transparent conductive layer by a micro-nano processing technology.
10. The method for manufacturing a transparent antenna according to claim 9, wherein in the step (2), a pre-prepared graphene film is transferred onto the dielectric layer or the metal nano network, or the graphene film is directly grown on the dielectric layer or the metal nano network; and printing the metal nanowire solution on the dielectric layer or the graphene film by adopting a printing method for the metal nanowire network.
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