CN117979673A - Anti-corrosion transparent electromagnetic shielding film and preparation method and application thereof - Google Patents

Anti-corrosion transparent electromagnetic shielding film and preparation method and application thereof Download PDF

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CN117979673A
CN117979673A CN202410373003.3A CN202410373003A CN117979673A CN 117979673 A CN117979673 A CN 117979673A CN 202410373003 A CN202410373003 A CN 202410373003A CN 117979673 A CN117979673 A CN 117979673A
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dielectric layer
electromagnetic shielding
shielding film
transparent electromagnetic
corrosion
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CN117979673B (en
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陈强
杨欣华
邓乐淳
王文卓
罗发
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Northwestern Polytechnical University
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    • HELECTRICITY
    • H05ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05KPRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K9/00Screening of apparatus or components against electric or magnetic fields
    • H05K9/0073Shielding materials
    • H05K9/0081Electromagnetic shielding materials, e.g. EMI, RFI shielding
    • H05K9/0084Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
    • GPHYSICS
    • G06COMPUTING; CALCULATING OR COUNTING
    • G06FELECTRIC DIGITAL DATA PROCESSING
    • G06F3/00Input arrangements for transferring data to be processed into a form capable of being handled by the computer; Output arrangements for transferring data from processing unit to output unit, e.g. interface arrangements
    • G06F3/01Input arrangements or combined input and output arrangements for interaction between user and computer
    • G06F3/03Arrangements for converting the position or the displacement of a member into a coded form
    • G06F3/041Digitisers, e.g. for touch screens or touch pads, characterised by the transducing means
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B13/00Apparatus or processes specially adapted for manufacturing conductors or cables
    • H01B13/0026Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01BCABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B5/00Non-insulated conductors or conductive bodies characterised by their form
    • H01B5/14Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports

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Abstract

The invention discloses an anti-corrosion transparent electromagnetic shielding film, a preparation method and application thereof, and relates to the technical field of electromagnetic shielding. The transparent electromagnetic shielding film comprises a first dielectric layer, a conductive layer, a second dielectric layer and a substrate which are sequentially laminated from top to bottom; the first dielectric layer comprises one or more of indium tin oxide, zinc oxide, aluminum oxide and zirconium dioxide; the second dielectric layer comprises one or more of indium tin oxide, zinc oxide, aluminum oxide, silicon dioxide and titanium dioxide. The invention introduces a plurality of interfaces on the transparent conductive multilayer structure on the surface of the substrate, can realize the repeated reflection loss of electromagnetic waves and achieves the optimal shielding effect.

Description

Anti-corrosion transparent electromagnetic shielding film and preparation method and application thereof
Technical Field
The invention relates to the technical field of electromagnetic shielding, in particular to an anti-corrosion transparent electromagnetic shielding film, and a preparation method and application thereof.
Background
The continuous development and alternation of electromagnetic wave technology makes the electromagnetic space environment increasingly complex. In unordered competition development modes of various electromagnetic facilities, the total energy of electromagnetic spectrum radiation on the earth surface is rapidly increased, and spectrum conflict is rapidly increased, so that the electromagnetic environment is rapidly deteriorated. The complexity of the electromagnetic environment brings serious electromagnetic radiation pollution problems, wherein the most main electromagnetic interference activities not only can influence the normal use and privacy protection of the electronic equipment, but also can cause irreversible damage and harm to organs such as the nervous system, the heart, the muscles and the like of the human body. In response to the current electromagnetic radiation pollution problem, electromagnetic shielding technology has been closely concerned and studied. However, it is a hotspot and difficulty of research as to how to achieve electromagnetic shielding targets at the optical window.
In view of the fact that light and microwaves belong to electromagnetic waves, the essence of transparent electromagnetic shielding is to realize the passband of an optical band and the stopband of a microwave band. Therefore, the research on the heat fire on the electromagnetic shielding material with good visible light transmittance and excellent electromagnetic shielding performance is endless. The transparent electromagnetic shielding material consists of a substrate, a conductive layer and an anti-reflection layer, wherein the electrical property of the conductive layer is a key factor for determining the electromagnetic shielding efficiency of the film, and the n and k coefficients of the anti-reflection layer influence the transmittance of the final film in the visible light wave band. The person skilled in the art adopts a zinc oxide/silver/zinc oxide multilayer structure design, and electromagnetic shielding effectiveness of up to 32dB and better mechanical performance are also obtained in the X wave band under the condition of obtaining high light transmittance of 90 percent. The prior art provides a nickel-silver-plated nanowire-based film, and finally the transparent electromagnetic shielding film material has the transmittance of 78.1% at 550nm, and the electromagnetic shielding effectiveness changes to 20.01dB and 16.62dB before and after corrosion, but the scheme still has the problems of insufficient shielding effectiveness and low transmittance. The currently reported nano-scale metallic silver film has high chemical activity, and is subject to the problem of failure caused by easy oxidation in severe environments (ocean, polar region and the like), and the research on environmental stability still has the defects and shortages. The prior art generally adopts the following ways for improving the corrosion resistance of the metallic silver film: (1) By coating the outer layer with a polymer such as various resins, and the effect of rejecting external corrosion can be achieved, the thickness of the coated film is significantly increased, and the advantage of "thinness" is lost. (2) The metal film can grow stably by doping the inhibitor with higher surface energy, so that a denser and flatter conductive layer is obtained, and the conductive layer has good weather resistance in a gas environment, but once immersed in a corrosive solution, the surface of the conductive layer can absorb water oxygen molecules to be corroded and then lose efficacy.
Therefore, development of a transparent conductive film with broadband, high strength, high transmittance and corrosion resistance in a radar band becomes a technical problem to be solved in the field.
Disclosure of Invention
Aiming at the defects in the background technology, the invention mainly solves the problems of insufficient shielding effectiveness and low light transmittance of materials and failure caused by easy oxidation in a severe environment in the prior art. The invention provides an anti-corrosion transparent electromagnetic shielding film, a preparation method and application thereof. The transparent conductive multilayer structure of the film on the surface of the substrate introduces a plurality of interfaces, so that the repeated reflection loss of electromagnetic waves can be realized, and the optimal shielding effect can be achieved.
The first object of the invention is to provide an anti-corrosion transparent electromagnetic shielding film, which comprises a first dielectric layer, a conductive layer, a second dielectric layer and a substrate, wherein the first dielectric layer, the conductive layer, the second dielectric layer and the substrate are sequentially arranged from top to bottom in a lamination manner;
The first dielectric layer comprises one or more of indium tin oxide, zinc oxide, aluminum oxide and zirconium dioxide; the second dielectric layer comprises one or more of indium tin oxide, zinc oxide, aluminum oxide, silicon dioxide and titanium dioxide.
Preferably, the thickness of the first dielectric layer is 35-55 nm; the thickness of the second dielectric layer is 40-60 nm.
Preferably, the conductive layer is one or more of silver, copper, gold, platinum, aluminum and iron; the thickness of the conductive layer is 8-12 nm.
Preferably, the substrate is float glass, polymethyl methacrylate or quartz glass.
Preferably, the transparent electromagnetic shielding film further comprises a surface hydrophobic layer, and the surface hydrophobic layer is arranged on the first dielectric layer.
Preferably, the surface hydrophobic layer is one or more of polydimethylsiloxane, polyacrylate and polytetrafluoroethylene; the thickness of the surface hydrophobic layer is 1-100 mu m.
The second object of the invention is to provide a preparation method of the anti-corrosion transparent electromagnetic shielding film, which comprises the following steps: sequentially preparing a second dielectric layer, a conductive layer and a first dielectric layer on a substrate by adopting a magnetron sputtering method; the substrate is ultrasonically cleaned in acetone, alcohol and deionized water, respectively, and dried in a vacuum oven before use.
The third object of the invention is to provide a preparation method of the anti-corrosion transparent electromagnetic shielding film, which comprises the following steps: sequentially preparing a second dielectric layer, a conductive layer and a first dielectric layer on a substrate by adopting a magnetron sputtering method; preparing a surface hydrophobic layer on the surface of the first dielectric layer by a spin coating method; the substrate is ultrasonically cleaned in acetone, alcohol and deionized water, respectively, and dried in a vacuum oven before use.
The fourth object of the invention is to provide an application of the anti-corrosion transparent electromagnetic shielding film in an electronic touch screen.
Compared with the prior art, the invention has the beneficial effects that:
The invention provides an anti-corrosion transparent electromagnetic shielding film, a preparation method and application thereof. According to the invention, the anti-corrosion transparent electromagnetic shielding film is obtained by sequentially laminating the first dielectric layer, the conductive layer and the second dielectric layer on the substrate from top to bottom, the conductive layer can realize effective loss of electromagnetic waves of 8 GHz-18 GHz of radar wave band, electromagnetic shielding performance is achieved, the first dielectric layer and the second dielectric layer regulate and control reflection behaviors of the conductive layer in the visible light range, and the observation effect of the transparent conductive film is ensured. Meanwhile, the second dielectric layer is used as a transition layer to improve the three-dimensional island growth mode of the conductive layer, the strong adhesive force, chemical stability and nucleation seed crystal characteristics of the conductive layer film to the substrate are improved, and the first dielectric layer can achieve the effects of reflection and reflection reduction based on the interference cancellation principle.
The invention also provides a surface hydrophobic layer on the first dielectric layer, and prepares the anti-corrosion transparent electromagnetic shielding film, so as to obtain a multilayer structure of the surface hydrophobic layer/the first dielectric layer/the conductive layer/the second dielectric layer, wherein the surface hydrophobic layer can isolate the water-oxygen environment, and the environmental stability of the transparent electromagnetic shielding function is improved. Compared with the existing electromagnetic shielding coating material, the transparent electromagnetic shielding film material provided by the invention has the advantages of excellent electromagnetic shielding performance, good light transmittance, corrosion resistance, low cost and the like.
Drawings
Fig. 1 is a schematic structural diagram of an electromagnetic shielding film with an uncoated surface hydrophobic layer provided by the invention.
Fig. 2 is a schematic structural diagram of an electromagnetic shielding film coated with a surface hydrophobic layer according to the present invention.
Fig. 3 is a graph showing the contrast of shielding effectiveness of the anti-corrosive transparent electromagnetic shielding films provided in examples 1, 6 and 7.
Fig. 4 is a graph showing the actual visible light transmittance of the anti-corrosive transparent electromagnetic shielding films provided in examples 1,6 and 7.
Fig. 5 is a water contact angle histogram of the anti-corrosive transparent electromagnetic shielding films provided in example 1 and example 4.
FIG. 6 is an electrochemical performance graph of the corrosion-resistant transparent electromagnetic shielding films provided in examples 1 and 4; in fig. 6, (a), (b), (c) and (d) are nyquist diagrams, bode mode diagrams, bode phase diagrams and potential polarization graphs of the anti-corrosion transparent electromagnetic shielding films provided in examples 1 and 4, respectively.
Fig. 7 is a partial enlarged view of fig. 6 (a).
Detailed Description
In order that those skilled in the art will better understand the technical solution of the present invention, the present invention will be further described with reference to the specific examples and the accompanying drawings, but the examples are not intended to be limiting.
The invention discloses a corrosion-resistant transparent electromagnetic shielding film and a preparation method thereof. By adopting the method, not only the electromagnetic shielding function can be realized, but also the problem that the reflectivity of the metallic silver film in the visible light wave band is high can be effectively solved. The product of the invention has excellent corrosion resistance, effectively prolongs the service life of the transparent electromagnetic shielding material at the optical window, and is expected to be applied to the external electromagnetic shielding protection of electronic equipment.
As described with reference to fig. 1, a first aspect of the present invention provides an anti-corrosion transparent electromagnetic shielding film, where the transparent electromagnetic shielding film includes a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3, and a substrate 4 sequentially stacked from top to bottom;
The first dielectric layer 1 comprises one or more of Indium Tin Oxide (ITO), zinc oxide, aluminum oxide and zirconium dioxide; the second dielectric layer 3 comprises one or more of Indium Tin Oxide (ITO), zinc oxide, aluminum oxide, silicon dioxide, and titanium dioxide. The thickness of the first dielectric layer 1 is 35-55 nm; the thickness of the second dielectric layer 3 is 40-60 nm.
The conductive layer 2 is one or more of silver, copper, gold, platinum, aluminum and iron; the thickness of the conductive layer 2 is 8-12 nm.
In the present invention, at least the sheet resistance of the transparent conductive layer 2 on the surface of the substrate is ensured to be less than 10Ω/Sq, preferably 5Ω/Sq. The substrate 4 is float glass, polymethyl methacrylate or quartz glass.
Referring to fig. 2, the transparent electromagnetic shielding film further includes a surface hydrophobic layer 5, and the surface hydrophobic layer 5 is disposed on the first dielectric layer 1.
The surface hydrophobic layer 5 is one or more of polydimethylsiloxane, polyacrylate and polytetrafluoroethylene; the thickness of the surface hydrophobic layer 5 is 1-100 mu m.
In the present invention, at least the light transmittance of the surface hydrophobic layer at 550nm is ensured to be more than 80%, preferably more than 90%; the hydrophobic angle is greater than 90 °, preferably greater than 105 °.
In one embodiment, the transparent conductive multilayer structure on the surface of the substrate introduces multiple interfaces, so that multiple reflection losses of electromagnetic waves can be realized, and the optimal shielding effect can be achieved. In addition, the thickness of the first dielectric layer/conductive layer/second dielectric layer system is optimized, when the reflected wave meets interference cancellation, the effects of reflection and reflection reduction in the visible light wave band can be realized, and the high requirements (the sheet resistance of the film is smaller than 10 ohms and the light transmittance is more than 90%) of the photoelectric performance of the film material are achieved in a coordinated manner.
The second aspect of the present invention provides a method for preparing an anti-corrosive transparent electromagnetic shielding film, comprising the steps of: sequentially preparing a second dielectric layer, a conductive layer and a first dielectric layer on a substrate by adopting a magnetron sputtering method; the substrate is ultrasonically cleaned in acetone, alcohol and deionized water, respectively, and dried in a vacuum oven before use.
The third aspect of the invention provides a method for preparing an anti-corrosion transparent electromagnetic shielding film, comprising the following steps: sequentially preparing a second dielectric layer, a conductive layer and a first dielectric layer on a substrate by adopting a magnetron sputtering method; preparing a surface hydrophobic layer on the surface of the first dielectric layer by a spin coating method; the substrate is ultrasonically cleaned in acetone, alcohol and deionized water, respectively, and dried in a vacuum oven before use.
The fourth aspect of the invention provides an application of the anti-corrosion transparent electromagnetic shielding film in an electronic touch screen.
It should be noted that, the experimental methods adopted in the invention are all conventional methods unless otherwise specified; the reagents and materials employed, unless otherwise specified, are commercially available.
Example 1
Referring to fig. 1, an anti-corrosion transparent electromagnetic shielding film comprises a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3 and a substrate 4 which are sequentially stacked from top to bottom; the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm; the thickness of the conductive layer was 8nm.
The substrate 4 is a 30mm by 30mm quartz glass substrate; the first dielectric layer 1 adopts ITO; ag is adopted as the conductive layer 2; the second dielectric layer 3 is made of ITO.
The preparation method comprises the following steps:
Firstly, respectively ultrasonically cleaning a quartz glass substrate with the thickness of 30mm multiplied by 30mm in deionized water, acetone and absolute ethyl alcohol for 10min, and drying in a vacuum oven after the ultrasonic cleaning is finished. And sequentially depositing a second dielectric layer, a conductive layer and a first dielectric layer on the surface of the substrate by adopting a magnetron sputtering method.
In the embodiment, the first dielectric layer and the second dielectric layer are both made of ITO, a power supply of magnetron sputtering is a radio frequency power supply, the power is 100W, the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm;
the conductive layer adopts Ag, the magnetron sputtering power supply adopts a direct current power supply, the power is 50W, and the thickness of the Ag layer is 8nm.
All sputtering was performed under an argon atmosphere with a gas flow rate controlled at 32Sccm.
The anti-corrosion transparent electromagnetic shielding film is called ITO/Ag/ITO (IAI) for short, and the specification is that a first dielectric layer/a conductive layer/a second dielectric layer (40 nm/8nm/44 nm).
The electromagnetic shielding film obtained in this embodiment is tested under the following test conditions: the sheet resistance of the film surface is obtained by a four-probe method; the electromagnetic shielding performance is tested (Agilent Technologies E-8362B) by a vector network analyzer, and the test frequency range is 8-18 GHz; the visible light transmittance was measured by an ultraviolet-visible-near infrared spectrophotometer (PERKINELMER LAMBDA 1050+). Electrochemical testing the results were obtained by means of an electrochemical workstation (CS 310X multichannel electrochemical workstation) with a working area of 1X 1cm 2. The results are shown in FIGS. 3,4 and 5.
Example 2
Referring to fig. 1, an anti-corrosion transparent electromagnetic shielding film comprises a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3 and a substrate 4 which are sequentially stacked from top to bottom; the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm; the thickness of the conductive layer was 10nm.
The substrate 4 is a 30mm by 30mm quartz glass substrate; the first dielectric layer 1 adopts ITO; ag is adopted as the conductive layer 2; the second dielectric layer 3 is made of ITO.
The preparation method comprises the following steps:
Firstly, respectively ultrasonically cleaning a quartz glass substrate with the thickness of 30mm multiplied by 30mm in deionized water, acetone and absolute ethyl alcohol for 10min, and drying in a vacuum oven after the ultrasonic cleaning is finished. And sequentially depositing a second dielectric layer, a conductive layer and a first dielectric layer on the surface of the substrate by adopting a magnetron sputtering method.
In this embodiment, the first dielectric layer and the second dielectric layer are both made of ITO, the magnetron sputtering power supply is a radio frequency power supply, the power is 100W, the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm.
The conductive layer adopts Ag, the magnetron sputtering power supply adopts a direct current power supply, the power is 50W, and the thickness of the Ag layer is 10nm.
All sputtering was performed under an argon atmosphere with a gas flow rate controlled at 32Sccm.
The anti-corrosion transparent electromagnetic shielding film is called ITO/Ag/ITO (IAI) for short, and the specification is that a first dielectric layer/a conductive layer/a second dielectric layer (40 nm/10nm/44 nm).
The electromagnetic shielding film obtained in this embodiment is tested under the following test conditions: the electromagnetic shielding performance is tested (Agilent Technologies E8362B) through a vector network analyzer, and the test frequency range is 2-18 GHz; the visible light transmittance was measured by an ultraviolet-visible-near infrared spectrophotometer (PERKINELMER LAMBDA 1050+). Electrochemical testing the results were obtained by means of an electrochemical workstation (CS 310X multichannel electrochemical workstation) with a working area of 1X 1cm 2.
Through tests, the transparent electromagnetic shielding film prepared in the embodiment has Fang Zu 6.45.45 omega/Sq, the light transmittance at the wavelength of 550nm of 87.83%, the average electromagnetic shielding efficiency of 8-18 GHz of 30dB, and the self-corrosion potential and the self-corrosion current of-0.43179V and-8.75A respectively.
Example 3
Referring to fig. 1, an anti-corrosion transparent electromagnetic shielding film comprises a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3 and a substrate 4 which are sequentially stacked from top to bottom; the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm; the conductive layer is 12nm.
The substrate 4 is a 30mm by 30mm quartz glass substrate; the first dielectric layer 1 adopts ITO; ag is adopted as the conductive layer 2; the second dielectric layer 3 is made of ITO.
The preparation method comprises the following steps:
Firstly, respectively ultrasonically cleaning a quartz glass substrate with the thickness of 30mm multiplied by 30mm in deionized water, acetone and absolute ethyl alcohol for 10min, and drying in a vacuum oven after the ultrasonic cleaning is finished. And sequentially depositing a second dielectric layer, a conductive layer and a first dielectric layer on the surface of the substrate by adopting a magnetron sputtering method.
In the embodiment, the first dielectric layer and the second dielectric layer are both made of ITO, a power supply of magnetron sputtering is a radio frequency power supply, the power is 100W, the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm;
The conductive layer adopts Ag, the magnetron sputtering power supply adopts a direct current power supply, the power is 50W, and the thickness of the Ag layer is 12nm.
All sputtering was performed under an argon atmosphere with a gas flow rate controlled at 32Sccm.
The anti-corrosion transparent electromagnetic shielding film is called ITO/Ag/ITO (IAI) for short, and the specification is that a first dielectric layer/a conductive layer/a second dielectric layer (40 nm/12nm/44 nm).
The electromagnetic shielding film obtained in this embodiment is tested under the following test conditions: the electromagnetic shielding performance is tested (Agilent Technologies E8362B) through a vector network analyzer, and the test frequency range is 2-18 GHz; the visible light transmittance was measured by an ultraviolet-visible-near infrared spectrophotometer (PERKINELMER LAMBDA 1050+). Electrochemical testing the results were obtained by means of an electrochemical workstation (CS 310X multichannel electrochemical workstation) with a working area of 1X 1cm 2.
Through tests, the transparent electromagnetic shielding film prepared in the embodiment has Fang Zu 6.06.06 omega/Sq, the light transmittance at the wavelength of 550nm of 91.56%, the average electromagnetic shielding efficiency of 8-18 GHz of 38dB, and the self-corrosion potential and the self-corrosion current of-0.40349V and-8.5A respectively.
Example 4
Referring to fig. 2, an anti-corrosion transparent electromagnetic shielding film comprises a surface hydrophobic layer 5, a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3 and a substrate 4 which are sequentially laminated from top to bottom; the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm; a conductive layer 8nm; the thickness of the surface hydrophobic layer was 36. Mu.m.
The substrate 4 is a 30mm by 30mm quartz glass substrate; the first dielectric layer 1 adopts ITO; ag is adopted as the conductive layer 2; the second dielectric layer 3 adopts ITO; the surface hydrophobic layer 5 is Polydimethylsiloxane (PDMS).
The preparation method comprises the following steps:
Firstly, respectively ultrasonically cleaning a quartz glass substrate with the thickness of 30mm multiplied by 30mm in deionized water, acetone and absolute ethyl alcohol for 10min, and drying in a vacuum oven after the ultrasonic cleaning is finished. And sequentially depositing a second dielectric layer, a conductive layer and a first dielectric layer on the surface of the substrate by adopting a magnetron sputtering method.
In the embodiment, the first dielectric layer and the second dielectric layer are both made of ITO, a power supply of magnetron sputtering is a radio frequency power supply, the power is 100W, the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm;
the conductive layer adopts Ag, the magnetron sputtering power supply adopts a direct current power supply, the power is 50W, and the thickness of the Ag layer is 8nm.
Finally, preparing a surface hydrophobic layer of ultrathin polydimethylsiloxane on the surface of the first dielectric layer by adopting a spin coating method, wherein the rotating speed is 1670r/min, the spin coating time is 18S, and the anticorrosive transparent conductive film is obtained after curing for 24 hours at 80 ℃, namely the PDMS/ITO/Ag/ITO, and the specification is a surface hydrophobic layer/the first dielectric layer/the conductive layer/the second dielectric layer (PDMS/40 nm/8nm/44 nm).
Through tests, the transmittance of the corrosion-resistant transparent electromagnetic shielding film prepared in the embodiment at 550nm is 88.08%, the average electromagnetic shielding efficiency of 8-18 GHz is 34dB, and the self-corrosion potential and the self-corrosion current are respectively-0.351V and-10.5A.
Example 5
Referring to fig. 1, an anti-corrosion transparent electromagnetic shielding film comprises a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3 and a substrate 4 which are sequentially stacked from top to bottom; the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm; the thickness of the conductive layer was 8nm.
The substrate 4 is a 30mm by 30mm quartz glass substrate; znO is adopted as the first dielectric layer 1; the conductive layer 2 adopts Cu; the second dielectric layer 3 adopts ZnO.
The preparation method comprises the following steps:
Firstly, respectively ultrasonically cleaning a quartz glass substrate with the thickness of 30mm multiplied by 30mm in deionized water, acetone and absolute ethyl alcohol for 10min, and drying in a vacuum oven after the ultrasonic cleaning is finished. And sequentially depositing a second dielectric layer, a conductive layer and a first dielectric layer on the surface of the substrate by adopting a magnetron sputtering method.
In the embodiment, znO is adopted for both the first dielectric layer and the second dielectric layer, a radio frequency power supply is adopted for a power supply of magnetron sputtering, the power is 100W, the thickness of the first dielectric layer is 40nm, and the thickness of the second dielectric layer is 44nm;
The conductive layer adopts Cu, the power supply of magnetron sputtering adopts a direct current power supply, the power is 50W, and the thickness of the Cu layer is 8nm.
All sputtering was performed under an argon atmosphere with a gas flow rate controlled at 32Sccm.
The anti-corrosion transparent electromagnetic shielding film is obtained, namely ZnO/Cu/ZnO (IAI) for short, and the specification is a first dielectric layer/a conductive layer/a second dielectric layer (40 nm/8nm/44 nm).
The electromagnetic shielding film obtained in this embodiment is tested under the following test conditions: the electromagnetic shielding performance is tested (Agilent Technologies E8362B) through a vector network analyzer, and the test frequency range is 2-18 GHz; the visible light transmittance was measured by an ultraviolet-visible-near infrared spectrophotometer (PERKINELMER LAMBDA 1050+). Electrochemical testing the results were obtained by means of an electrochemical workstation (CS 310X multichannel electrochemical workstation) with a working area of 1X 1cm 2.
Through tests, the transparent electromagnetic shielding film prepared in the embodiment has Fang Zu 8.05.05 omega/Sq, the light transmittance at the wavelength of 550nm of 88.20%, the average electromagnetic shielding efficiency of 8-18 GHz of 31dB, and the self-corrosion potential and the self-corrosion current of-0.513V and-9.05A respectively.
Example 6
The same as in example 1, except that the thickness of the first dielectric layer was 50nm and the thickness of the second dielectric layer was 45nm; the thickness of the conductive layer is 8nm
The anti-corrosion transparent electromagnetic shielding film is called ITO/Ag/ITO (IAI) for short, and the specification is that a first dielectric layer/a conductive layer/a second dielectric layer (50 nm/8nm/45 nm).
Example 7
The same as in example 1, except that the thickness of the first dielectric layer was 40nm and the thickness of the second dielectric layer was 50nm; the thickness of the conductive layer is 8nm
The anti-corrosion transparent electromagnetic shielding film is called ITO/Ag/ITO (IAI) for short, and the specification is that a first dielectric layer/a conductive layer/a second dielectric layer (40 nm/8nm/50 nm).
Comparative example 1
The anti-corrosion transparent electromagnetic shielding film comprises a first dielectric layer 1, a conductive layer 2, a second dielectric layer 3 and a substrate 4 which are sequentially stacked from top to bottom; the thickness of the first dielectric layer is 65nm, and the thickness of the second dielectric layer is 25nm; the thickness of the conductive layer was 8nm.
The substrate 4 is a 30mm by 30mm quartz glass substrate; the first dielectric layer 1 adopts ITO; ag is adopted as the conductive layer 2; the second dielectric layer 3 is made of ITO.
The preparation method comprises the following steps:
Firstly, respectively ultrasonically cleaning a quartz glass substrate with the thickness of 30mm multiplied by 30mm in deionized water, acetone and absolute ethyl alcohol for 10min, and drying in a vacuum oven after the ultrasonic cleaning is finished. And sequentially depositing a second dielectric layer, a conductive layer and a first dielectric layer on the surface of the substrate by adopting a magnetron sputtering method.
In the comparative example, the first dielectric layer and the second dielectric layer are both made of ITO, a power supply of magnetron sputtering is a radio frequency power supply, the power is 100W, the thickness of the first dielectric layer is 65nm, and the thickness of the second dielectric layer is 25nm;
the conductive layer adopts Ag, the magnetron sputtering power supply adopts a direct current power supply, the power is 50W, and the thickness of the Ag layer is 8nm.
All sputtering was performed under an argon atmosphere with a gas flow rate controlled at 32Sccm.
The electromagnetic shielding film obtained in this comparative example was tested under the following test conditions: the sheet resistance of the film surface is obtained by a four-probe method; the electromagnetic shielding performance is tested (Agilent Technologies E-8362B) by a vector network analyzer, and the test frequency range is 8-18 GHz; the visible light transmittance was measured by an ultraviolet-visible-near infrared spectrophotometer (PERKINELMER LAMBDA 1050+). Electrochemical testing the results were obtained by means of an electrochemical workstation (CS 310X multichannel electrochemical workstation) with a working area of 1X 1cm 2. Testing the electromagnetic shielding film prepared by the method, wherein the testing conditions are as follows: the electromagnetic shielding performance is tested (Agilent Technologies E8362B) through a vector network analyzer, and the test frequency range is 2-18 GHz; the visible light transmittance was measured by an ultraviolet-visible-near infrared spectrophotometer (PERKINELMER LAMBDA 1050+). Electrochemical testing the results were obtained by means of an electrochemical workstation (CS 310X multichannel electrochemical workstation) with a working area of 1X 1cm 2.
Through tests, the transparent electromagnetic shielding film prepared in the comparative example has Fang Zu 13.05.05 omega/Sq, the light transmittance at the wavelength of 550nm of 87.20%, the average electromagnetic shielding efficiency of 8-18 GHz of 28dB, and the self-corrosion potential and the self-corrosion current of-0.407V and-8.05A respectively.
In order to explain the related performance of the transparent electromagnetic shielding film provided by the invention, the transparent electromagnetic shielding film is described with reference to the accompanying drawings.
FIG. 3 is a graph showing the contrast of shielding effectiveness of the anti-corrosive transparent electromagnetic shielding films provided in examples 1, 6 and 7;
As can be seen from fig. 3, the single silver film Ag has an average shielding effectiveness of 23.5dB and 27.5dB in X, ku bands, respectively. The shielding effectiveness of the first dielectric layer/the conductive layer/the second dielectric layer obtained through structural modification is obviously improved in the 8-18GHz wave band, wherein when the first dielectric layer is 40nm and the second dielectric layer is 44nm, the average shielding effectiveness in X, ku wave bands is respectively optimal and respectively 32dB and 34dB. Meanwhile, the difference of the loss of the electromagnetic wave by the thin film is caused by changing the thickness of the first dielectric layer and the thickness of the second dielectric layer, because the reflection condition of the electromagnetic wave at the interface of the dielectric layer and the conductive layer is different from the reflection condition of the electromagnetic wave inside the thin film. Through comparison, the sandwich structure provided by the invention can greatly improve the shielding effectiveness of the single-layer silver film.
Fig. 4 is a graph showing the actual visible light transmittance of the anti-corrosive transparent electromagnetic shielding films provided in examples 1,6 and 7;
As can be seen from fig. 4, the transmittance of the single-layer silver film Ag at a wavelength of 550nm was about 65%. Compared with a single-layer silver film, the transmittance of IAI (40 nm/8nm/44 nm) at 550nm percent is 86.5 percent through the optimization of the thickness of the first dielectric layer and the second dielectric layer, and the optimal visible light wave band transmittance is obtained. It can be seen that the indium tin oxide/silver/indium tin oxide multilayer nanofilm exhibited good optical permeability.
Fig. 5 is a water contact angle histogram of the anti-corrosive transparent electromagnetic shielding film provided in example 1 and example 4; as can be seen from fig. 5, the water contact angles of the anti-corrosive transparent electromagnetic shielding film provided in example 1 and the anti-corrosive transparent electromagnetic shielding film provided in example 4 were tested, and it was found that after PDMS was coated on the surface, the film was changed from a hydrophilic state to a hydrophobic state, and the water contact angle was raised from 64 ° to 114 °, thus imparting water repellency to the film and realizing anti-oxidation protection to the silver film.
FIG. 6 is an electrochemical performance graph of the corrosion-resistant transparent electromagnetic shielding films provided in examples 1 and 4; FIG. 7 is an enlarged view of a portion of FIG. 6 (a); in fig. 6, (a), (b), (c) and (d) are nyquist diagrams, bode mode diagrams, bode phase diagrams and potential polarization graphs of the anti-corrosion transparent electromagnetic shielding films provided in examples 1 and 4, respectively.
From fig. 6 (a), the electrochemical behaviors of the anti-corrosion transparent electromagnetic shielding film provided in example 1 and the anti-corrosion transparent electromagnetic shielding film provided in example 4 in a 5% nacl solution are examined, and it can be seen from fig. 7 that the arc radius of the anti-corrosion transparent electromagnetic shielding film provided in example 4 is larger than that of the anti-corrosion transparent electromagnetic shielding film provided in example 1, that is, the impedance of the anti-corrosion transparent electromagnetic shielding film provided in example 4 is larger, and the anti-corrosion transparent electromagnetic shielding film exhibits more excellent corrosion resistance. As is clear from fig. 6 (b) and (c), it was found that the film resistance after spin-coating PDMS was greater, and the diffusion path of the secondary solution was blocked from direct contact with the highly active etching medium, thereby greatly improving the corrosion resistance. Meanwhile, in order to quantitatively illustrate the corrosion rate problem of the film, the measured potentiodynamic polarization curve of the film is shown in (d) of fig. 6, and a trend that the potentiodynamic polarization curve of the anti-corrosion transparent electromagnetic shielding film provided in example 4 is shifted from top right compared with that of the film provided in example 1 is observed, namely that potential rise occurs, the corrosion current density is reduced, namely that the electrochemical corrosion rate is slow, so that the PDMS has a good corrosion inhibition effect.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (9)

1. The anti-corrosion transparent electromagnetic shielding film is characterized by comprising a first dielectric layer, a conductive layer, a second dielectric layer and a substrate which are sequentially arranged from top to bottom in a lamination manner;
The first dielectric layer comprises one or more of indium tin oxide, zinc oxide, aluminum oxide and zirconium dioxide; the second dielectric layer comprises one or more of indium tin oxide, zinc oxide, aluminum oxide, silicon dioxide and titanium dioxide.
2. The anti-corrosion transparent electromagnetic shielding film according to claim 1, wherein the thickness of the first dielectric layer is 35-55 nm; the thickness of the second dielectric layer is 40-60 nm.
3. The corrosion resistant transparent electromagnetic shielding film of claim 1, wherein the conductive layer is one or more of silver, copper, gold, platinum, aluminum, iron; the thickness of the conductive layer is 8-12 nm.
4. The corrosion resistant transparent electromagnetic shielding film of claim 1, wherein the substrate is float glass, polymethyl methacrylate, or quartz glass.
5. The corrosion resistant transparent electromagnetic shielding film of claim 1, further comprising a surface hydrophobic layer disposed on the first dielectric layer.
6. The corrosion resistant transparent electromagnetic shielding film according to claim 5, wherein the surface hydrophobic layer is one or more of polydimethylsiloxane, polyacrylate, polytetrafluoroethylene; the thickness of the surface hydrophobic layer is 1-100 mu m.
7. A method for preparing the anti-corrosion transparent electromagnetic shielding film according to any one of claims 1 to 4, comprising the following steps: sequentially preparing a second dielectric layer, a conductive layer and a first dielectric layer on a substrate by adopting a magnetron sputtering method; the substrate is ultrasonically cleaned in acetone, alcohol and deionized water, respectively, and dried in a vacuum oven before use.
8. A method for preparing the anti-corrosive transparent electromagnetic shielding film according to claim 5 or 6, comprising the following steps: sequentially preparing a second dielectric layer, a conductive layer and a first dielectric layer on a substrate by adopting a magnetron sputtering method; preparing a surface hydrophobic layer on the surface of the first dielectric layer by a spin coating method; the substrate is ultrasonically cleaned in acetone, alcohol and deionized water, respectively, and dried in a vacuum oven before use.
9. An application of the anti-corrosion transparent electromagnetic shielding film according to any one of claims 1-6 in an electronic touch screen.
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