CN106413364A - Bidirectional wave absorption transparent electromagnetic shielding device based on graphene/transparent conductive films - Google Patents

Bidirectional wave absorption transparent electromagnetic shielding device based on graphene/transparent conductive films Download PDF

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CN106413364A
CN106413364A CN201510449163.2A CN201510449163A CN106413364A CN 106413364 A CN106413364 A CN 106413364A CN 201510449163 A CN201510449163 A CN 201510449163A CN 106413364 A CN106413364 A CN 106413364A
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transparent
graphene
layer
electromagnetic shielding
device based
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CN106413364B (en
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谭久彬
陆振刚
马栎敏
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Harbin Institute of Technology
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Harbin Institute of Technology
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Abstract

A bidirectional wave absorption transparent electromagnetic shielding device based on graphene/transparent conductive films belongs to the optical transparent member electromagnetic shielding technology field, and is formed by assembling a transparent absorption layer A, a transparent medium A, a transparent reflection layer, a transparent medium B and a transparent absorption layer B which are orderly laminated and parallelly configured. The transparent absorption layers A and B are both formed by 1-6 layers of graphene films separated by transparent mediums, and the transparent reflection layer is composed of transparent conductive films comprising transparent metal compound films, silver nanowire films or metal meshes. The electromagnetic shielding device can absorb the radio frequency radiation at the two sides of the devices simultaneously, repeatedly and strongly, thereby realizing the bidirectional strong shielding and low reflection characteristics. The electromagnetic shielding device of the present invention solves the problem that a conventional transparent electromagnetic shielding method can not consider the bidirectional low-electromagnetic reflection, the strong electromagnetic shielding and the high light transmission simultaneously, and has the characteristics of high light transmission performance, strong electromagnetic shielding and bidirectional low electromagnetic reflection.

Description

Based on Graphene / The two-way suction ripple transparency electromagnetic wave shield device of transparent conductive film
Technical field
The invention belongs to optical clear part electromagnetic shielding field, particularly to a kind of two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film.
Background technology
With the development of broadcast, TV, wireless communication technique and microwave technology, radio-frequency apparatus are equipped in a large number in each place of mankind's activity, and the continuous broadening of spectral range, and intensity is multiplied, and this not only interferes to electronic equipment, also health are produced and threaten.This invisible impalpable " electromagnetic pollution " directly acts on machine or human body, is to endanger serious " stealthy killer ", it has also become the fifth-largest pollution after atmospheric pollution, water pollution, noxious waste pollution and sound pollution.Electromagnetic shielding(Including absorption and reflection)It is the major measure of preventing and treating electromagnetic pollution, in recent years, electromangnetic spectrum gets more and more people's extensive concerning.The electromagnetic shielding wherein needing visual observation occasion is transparency electromagnetic wave shield, it is all difficult point and focus, Medical electromagnetic isolation room observation window, communication apparatus transparency electromagnetic wave shield element, Aero-Space equipment optical window, advanced optical instrument optical window, secured facilities anti-electromagnetic exposure optical window, LCDs, mobile phone touch, vehicle-mounted transparent antenna etc. are covered in its application all the time.
At present, realizing the difficult point of transparency electromagnetic wave shield, to essentially consist in traditional absorbing material mostly opaque or transparent very poor, and conditioned each other it is difficult to realize high transparent and forceful electric power magnetic shield simultaneously based on the transparency and conductive shield ability in the reflective transparent shield technology of transparent conductive material or device.Additionally, between ELECTROMAGNETIC RADIATION REFLECTION is made the return trip empty by conducting reflective Transparent shielding technology, causing " secondary pollution " to spatial environmentss, being unfavorable for the thorough preventing and treating of electromagnetic pollution.
In a lot of fields of modern technologies, material with carbon element all plays very important role, and in numerous allotropes of carbon, Graphene is the very typical material of one kind, and Graphene is with sp by carbon atom2Hybrid orbital forms the flat film that hexangle type is in honeycomb lattice, it is the two-dimensional material of only one of which carbon atom thickness, there is many-sided excellent property, one of prominent property is that have excellent transparent conductivity, also there is certain microwave absorbing property, this makes Graphene have very high using value in transparency electromagnetic wave shield field:
1. United States Patent (USP) US20130068521 " Electromagnetic shielding Method using graphene and electromagnetic shiedling material " is loaded on metallic plate, is realized electromagnetic shielding on polymer substrate using Graphene prepared by chemical vapour deposition technique (CVD); compared with the metallic plate not loading Graphene, polymer substrate; after loading Graphene, integrally-built electromagnetic shielding efficiency increases.
2. patent 201310232829. X " for shielding the structures and methods based on Graphene of electromagnetic radiation " describes a kind of electromagnetic armouring structure being more than 1 megahertz of electromagnetic radiation for screening frequencies, this structure is made up of one or more layers Graphene, and at least one of which Graphene is doped with dopant.
3. patent 201420099425.8 " a kind of transparency electromagnetic wave shield film based on graphene film " describes a kind of transparency electromagnetic wave shield film of nano-silver thread of arranging between transparent substrates and graphene film, nano-silver thread plays electric charge bridge beam action, increase the electric conductivity of whole electromagnetic shielding film, improve shield effectiveness.
4. the metallic mesh that James M. Tour of Rice Univ USA (Rice University) et al. is 5 μm with photoetching process prepares line bar width, and single-layer graphene is shifted on its surface, it is made for Graphene metallic mesh mixed conductor membranes(James M. Tour etc., " Rational Design of Hybrid Graphene Films for High-Performance Transparent Electrodes ". ACS Nano, 2011,5 (8):6472~6479), this mixed conductor membranes can achieve 90% light transmittance and the sheet resistance of 20 Ω/sq.
5. the shield effectiveness that Seul Ki Hong of Korea Advanced Institute of Science and Technology (KAIST) et al. reports single-layer graphene is 2.27dB(Hong S K etc., " Electromagnetic interference shielding effectiveness of monolayer graphene”. Nanotechnology, 2012, 23(45):455704), wherein absorption loss and reflection loss respectively -4.38dB and -13.66dB.
6. the Kim S of Korea S Cheng Jun shop university (Sungkyunkwan University) and Samsung Motor Corporation of Korea S (Samsung Electro-Mechanics Myeong-Gi Kim) et al. adopts Graphene (PEI/RGO) stepped construction of Polyetherimide/oxidation-reduction method preparation to realize electromagnetic shielding(Kim S etc., " Electromagnetic Interference (EMI) Transparent Shielding of Reduced Graphene Oxide (RGO) Interleaved Structure Fabricated by Electrophoretic Deposition”. ACS applied materials & interfaces, 2014, 6(20):17647-17653), the electromagnetic shielding efficiency of double-deck PEI/ RGO and monolayer PEI/ RGO stepped construction is respectively 6.37 dB and 3.09dB, and absorption loss accounts for the ratio respectively 96% and 92% of total electromagnetic shielding efficiency.
Graphene is used for electromagnetic shielding by above-mentioned each scheme, it is possible to achieve certain effectiveness.United States Patent (USP) US20130068521 adopts Graphene as the core devices of electromagnetic screen, and large-area for full wafer Graphene is transferred to by metal by the Graphene transfer method of roll-to-roll, on polymer substrate, achieve excellent effectiveness, but this electromagnetic shielding device does not have the transparency.Patent 201310232829. X " for shielding the structures and methods based on Graphene of electromagnetic radiation " is using graphene film as the main body of electromagnetic armouring structure, and wherein at least one layer graphene thin film is doped to improve electromagnetic shielding efficiency, but doping can affect integrally-built light transmittance.Patent 201420099425.8 " a kind of transparency electromagnetic wave shield film based on graphene film " utilizes nano-silver thread to improve the electrical conductivity of graphene film, increase the raising that reflection loss realizes electromagnetic shielding efficiency, but the main contributions of electromagnetic shielding are produced by reflection.In above-mentioned document 4, graphene film is loaded on formation Graphene and metallic mesh on metallic mesh and fit tightly structure, this arrangement enhances the electric conductivity of metallic mesh, light transmittance reaches 91%, but the electromagnetic shielding of this structure is based on reflecting simultaneously.In above-mentioned document 5, result of study shows, although the shield effectiveness of Graphene increases with the number of plies and is significantly increased, absorption loss increases seldom, and often increases by a layer graphene, transmission loss 2.3% is so that this structure is difficult to realize high printing opacity, low reflection and forceful electric power magnetic shield simultaneously.The graphene film (RGO) adopting oxidation-reduction method preparation in above-mentioned document 6 realizes electromagnetic shielding with Polyetherimide (PEI) stepped construction, and shield based on absorption loss, but the shield effectiveness of double-deck PEI/RGO structure is only 6.37dB, and light transmittance is only 62% it is difficult to realize forceful electric power magnetic shield and high printing opacity simultaneously.
In a word, in existing electromangnetic spectrum, the method based on reflection-type electromagnetic shielding easily causes secondary electromagnetic pollution;And there is the electromagnetic shielding method of absorption loss, or it is not high to there is light transmittance, or electromagnetic shielding efficiency strong it is difficult to realize high transparent and forceful electric power magnetic shield simultaneously.
Content of the invention
It is an object of the invention to overcoming the shortcomings of above-mentioned existing transparency electromagnetic wave shield technology, mutually restrict especially for the transparency and conductive shield ability in existing reflective transparent shield technology, it is difficult to take into account high transmission rate and strong micro-wave screening efficiency, and reflected electromagnetic signal causes the problem of electromagnetic exposure and secondary pollution, research and develop a kind of two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film, reach the purpose being provided simultaneously with two-way low ELECTROMAGNETIC REFLECTION, forceful electric power magnetic shield and high light transmittance energy.
The object of the present invention is achieved like this:Based on the two-way suction ripple transparency electromagnetic wave shield device of Graphene/transparent conductive film, described electromagnetic shielding device is made up of the transparent absorbent layer A of overlap and configured in parallel successively, transparent medium A, transparent reflecting layer, transparent medium B and transparent absorbent layer B assembling;The graphene film that described transparent absorbent layer A and B is separated by transparent medium by 1-6 layer is constituted, and transparent reflecting layer is made up of transparent conductive film, including transparent metal compound thin film, nano-silver thread thin film or metallic mesh.
The good result that the present invention produces focuses primarily upon realization and is provided simultaneously with two-way low ELECTROMAGNETIC REFLECTION, forceful electric power magnetic shield and high light transmittance energy, specific as follows:
Using the Microwave Absorption Properties of Graphene and the Microwave reflection characteristics of transparent conductive film, the two is organically combined, using transparent conductive film as transparent reflecting layer, realize the forceful electric power magnetoreflection to radio-frequency radiation;The graphene film structure being separated by transparent medium with 1-6 layer, as transparent absorbent layer, can make radio-frequency radiation partially absorb and be passed through in the form of low reflection;By two groups of transparent absorbent layers be respectively placed in transparent reflecting layer both sides so that through transparent absorbent layer microwave and transparent absorbent layer is returned in strong reflection, through reflection and multiple absorb, realize good electromagnetic shielding;Two groups of transparent absorbent layers are respectively placed in the both sides composition electromagnetic shielding device of transparent reflecting layer, absorb the radio-frequency radiation inside and outside electromagnetic shielding device simultaneously, make the radio-frequency radiation from electromagnetic shielding device both sides all pass through reflection and multiple absorption, finally realize two-way low reflection forceful electric power magnetic shield.
The multiple structure of the present invention, on the one hand due to the presence of transparent absorbent layer, solves the problems, such as that the shielding based on reflection during only transparent conductive film easily causes secondary electromagnetic pollution;On the other hand due to the presence of transparent reflecting layer and be placed between two groups of transparent absorbent layers, so that the microwave to be shielded from electromagnetic shielding device both sides all can absorb through reflection with repeatedly, not only solve shield effectiveness not high problem when only existing graphene film absorbed layer, there is two-way shielding action, and two-way shielding action is all based on absorbing;Meanwhile, for light wave, only transmit transparent absorbent layer and transparent reflecting layer once, the loss that it occurs is less, can achieve high light transmission features.
To sum up, the present invention can realize being provided simultaneously with the most prominent effect that two-way low ELECTROMAGNETIC REFLECTION, forceful electric power magnetic shield and high light transmittance can be the present invention.
Brief description
Fig. 1 is the generalized section of the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film.
Fig. 2 is the grid unit arrangement mode structural representation of grid metallic mesh.
Fig. 3 is the grid unit arrangement mode structural representation of annulus metallic mesh.
Fig. 4 is the grid unit arrangement mode structural representation of multicycle micro-loop metallic mesh.
Fig. 5 is the generalized section of the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film described in embodiment.
Fig. 6 is the structural representation of the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film described in embodiment.
In figure piece number explanation:1. protective layer A 2. anti-reflection film A 3. transparent absorbent layer A 4. transparent medium A, 5. transparent reflecting layer, 6. transparent medium B 7. transparent absorbent layer B 8. anti-reflection film B, 9. protective layer B, 10. graphene film A, 11. transparent medium C, 12. graphene film B, 13. graphene film C 14. micro-loop metallic mesh.
Specific embodiment
Below in conjunction with the accompanying drawings embodiment of the present invention is described in detail:
Described electromagnetic shielding device is made up of the transparent absorbent layer A3 of overlap and configured in parallel successively, transparent medium A4, transparent reflecting layer 5, transparent medium B6 and transparent absorbent layer B7 assembling;The graphene film that described transparent absorbent layer A3 and B7 is separated by transparent medium by 1-6 layer is constituted, and transparent reflecting layer 5 is made up of transparent conductive film, including transparent metal compound thin film, nano-silver thread thin film or metallic mesh.
The protective layer A1 of the anti-reflection film A2 of configured in parallel single or multiple lift and single or multiple lift successively on transparent absorbent layer A3 lateral part;The protective layer B9 of the anti-reflection film B8 of configured in parallel single or multiple lift and single or multiple lift successively on transparent absorbent layer B7 lateral part.
Constitute the number of plies of Graphene that the graphene film of transparent absorbent layer A3 and B7 comprises be monolayer, double-deck or three layers, and the Graphene number of plies that the graphene film that separated by transparent medium of each layer comprises can be identical or different.
The light transmittance of transparent reflecting layer 5 is more than 90%.
If transparent reflecting layer 5 is made up of metallic mesh, described metallic mesh is made up of by the two-dimension plane structure of periodic arrangement grid unit, the cycle of grid unit is submillimeter to millimeter magnitude, metal wire width is submicron to micron dimension, the connection metal being overlapped by metal wire between adjacent grid unit or connecting two metal line bars in the setting of overlapping place.
If transparent reflecting layer 5 is made up of metallic mesh, metallic mesh is made up of the good alloy material of electric conductivity, and alloy thickness is more than 100nm.
Described transparent medium A4, transparent medium B6 and separation transparent absorbent layer A3, the transparent medium making material of transparent absorbent layer B7 graphene film include simple glass, quartz glass, infra-red material and transparent resin material.
The two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film of the present invention, transparent reflecting layer 5 is the core devices realizing strong reflection electromagnetic shielding, and transparent absorbent layer A3 and B7 has the low characteristic reflecting and partially absorb microwave.Two groups of transparent absorbent layer A3 and B7 are located at the both sides of transparent reflecting layer 5 so that the electromagnetic shielding device of this structure can take into account the radio-frequency radiation that shielding absorbs device both sides simultaneously.Taking positioned at the radio-frequency radiation wave source outside electromagnetic shielding device transparent absorbent layer A3 as a example, the radio-frequency radiation energy being irradiated to electromagnetic shielding device enters transparent absorbent layer A3, energy after layer graphene film absorption each in transparent absorbent layer A3, decay is by transparent reflecting layer 5 high reflection, radio-frequency radiation after reflection, again through transparent absorbent layer A3, again passes by the attenuation by absorption of wherein each layer graphene thin film;A small amount of radio-frequency radiation through transparent reflecting layer 5 transmission enters the transparent absorbent layer B7 being located at transparent reflecting layer 5 opposite side and by wherein each layer graphene film absorption, decay, and experience multiple reflections and absorption in the reflecting part of each graphene film layer and transparent dielectric layer again, so that most energy of radio-frequency radiation is absorbed.If radio-frequency radiation is derived from outside transparent absorbent layer B7, the shielding of generation and Absorption are similar to outside transparent absorbent layer A3, thus the electromagnetic shielding device of the present invention can achieve the electromagnetic shielding based on two-way absorption.And the optical region that needs are passed through, merely through transparent absorbent layer A3 and B7 once with transparent reflecting layer 5 once, the loss that it occurs is less, enables high printing opacity.
Embodiment
Electromagnetic shielding device is made up of the transparent absorbent layer A 3 of overlap and configured in parallel successively, transparent medium A 4, transparent reflecting layer 5, transparent medium B6 and transparent absorbent layer B7 assembling;Described transparent absorbent layer A3 is made up of the graphene film B12 of the graphene film A10, transparent medium C11 and monolayer of the monolayer of configured in parallel successively, transparent reflecting layer is made up of micro-loop metallic mesh 14, and transparent absorbent layer B7 is made up of the graphene film C13 of one layer of monolayer.
The solution have the advantages that:When the electromagnetic shielding efficiency of metallic mesh is 19.0dB, the electromagnetic shielding efficiency of the present invention is 23.7dB, if radio-frequency radiation is derived from outside electromagnetic shielding device transparent absorbent layer A3, absorption loss accounts for the 58.6% of total shielding energy;If radio-frequency radiation is derived from outside electromagnetic shielding device transparent absorbent layer B7, absorption loss accounts for the 41.0% of total shielding energy;Radio-frequency radiation for the electromagnetic shielding device both sides of this structure all achieves forceful electric power magnetic shield, and the graphene film number of plies is more, and absorption loss proportion is bigger;And light transmittance is 88.1%, still has high light transmission features.
The also corresponding in addition several embodiments of the present invention, metallic mesh in Fig. 5 is changed to transparent conductive metal compound film or nano-silver thread thin film, and keeps original each layer arrangement mode constant, finally also can obtain similar effects;Increase or decrease the graphene film number of plies being separated by transparent medium of transparent absorbent layer in Fig. 5, it will lead to the increase of absorption loss or the raising of light transmittance, can adjust accordingly according to actual needs.

Claims (7)

1. the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film it is characterised in that:Described electromagnetic shielding device is made up of transparent absorbent layer A (3) of overlap and configured in parallel successively, transparent medium A (4), transparent reflecting layer (5), transparent medium B (6) and transparent absorbent layer B (7) assembling;The graphene film that described transparent absorbent layer A (3) and B (7) are separated by transparent medium by 1-6 layer is constituted, transparent reflecting layer (5) is made up of transparent conductive film, including transparent metal compound thin film, nano-silver thread thin film or metallic mesh.
2. the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film according to claim 1 it is characterised in that:The protective layer A (1) of the anti-reflection film A (2) of configured in parallel single or multiple lift and single or multiple lift successively on transparent absorbent layer A (3) lateral part;The protective layer B (9) of the anti-reflection film B (8) of configured in parallel single or multiple lift and single or multiple lift successively on transparent absorbent layer B (7) lateral part.
3. the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film according to claim 1 it is characterised in that:Constitute the number of plies of Graphene that the graphene film of transparent absorbent layer A (3) and B (7) comprises be monolayer, bilayer or three layers, and the Graphene number of plies that the graphene film that separated by transparent medium of each layer comprises can be identical or different.
4. the transparency electromagnetic wave shield device based on Graphene/metallic mesh interlayer stepped construction according to claim 1 it is characterised in that:The light transmittance of transparent reflecting layer (5) is more than 90%.
5. the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film according to claim 1 it is characterised in that:If transparent reflecting layer (5) is made up of metallic mesh, described metallic mesh is made up of by the two-dimension plane structure of periodic arrangement grid unit, the cycle of grid unit is submillimeter to millimeter magnitude, metal wire width is submicron to micron dimension, the connection metal being overlapped by metal wire between adjacent grid unit or connecting two metal line bars in the setting of overlapping place.
6. the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film according to claim 1 it is characterised in that:If transparent reflecting layer (5) is made up of metallic mesh, metallic mesh is made up of the good alloy material of electric conductivity, and alloy thickness is more than 100nm.
7. the two-way suction ripple transparency electromagnetic wave shield device based on Graphene/transparent conductive film according to claim 1 it is characterised in that:The transparent medium making material of described transparent medium A, B (4,6) and separation transparent absorbent layer A, B (3,7) graphene film includes simple glass, quartz glass, infra-red material and transparent resin material.
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Cited By (4)

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CN111625149A (en) * 2020-06-03 2020-09-04 上海天马微电子有限公司 Conductive shielding module, manufacturing method thereof and display device
CN111628297A (en) * 2020-06-23 2020-09-04 航天科工武汉磁电有限责任公司 Broadband transparent wave-absorbing material based on double-layer conductive film
CN112265292A (en) * 2020-08-21 2021-01-26 成都飞机工业(集团)有限责任公司 Forming method of graphene wave-absorbing composite material skin
CN113079683A (en) * 2020-01-06 2021-07-06 宁波材料所杭州湾研究院 High-light-transmission electromagnetic shielding film and preparation method thereof

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Publication number Priority date Publication date Assignee Title
CN113079683A (en) * 2020-01-06 2021-07-06 宁波材料所杭州湾研究院 High-light-transmission electromagnetic shielding film and preparation method thereof
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CN112265292A (en) * 2020-08-21 2021-01-26 成都飞机工业(集团)有限责任公司 Forming method of graphene wave-absorbing composite material skin

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