CN106653931B - Graphene-based infra-red electromagnetic shielding filter, zinc sulphide window and preparation method thereof - Google Patents
Graphene-based infra-red electromagnetic shielding filter, zinc sulphide window and preparation method thereof Download PDFInfo
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- CN106653931B CN106653931B CN201611224658.6A CN201611224658A CN106653931B CN 106653931 B CN106653931 B CN 106653931B CN 201611224658 A CN201611224658 A CN 201611224658A CN 106653931 B CN106653931 B CN 106653931B
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 76
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 56
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000011889 copper foil Substances 0.000 claims abstract description 59
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 54
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 54
- 230000007704 transition Effects 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 11
- 239000000969 carrier Substances 0.000 claims abstract description 10
- 238000007711 solidification Methods 0.000 claims abstract description 9
- 230000008023 solidification Effects 0.000 claims abstract description 9
- 229920000642 polymer Polymers 0.000 claims abstract description 6
- 239000007921 spray Substances 0.000 claims abstract description 6
- 238000005507 spraying Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 53
- 229920002120 photoresistant polymer Polymers 0.000 claims description 18
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 10
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 10
- URQUNWYOBNUYJQ-UHFFFAOYSA-N diazonaphthoquinone Chemical compound C1=CC=C2C(=O)C(=[N]=[N])C=CC2=C1 URQUNWYOBNUYJQ-UHFFFAOYSA-N 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 238000005530 etching Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000003708 ampul Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 8
- 239000010949 copper Substances 0.000 claims description 8
- 239000010453 quartz Substances 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 230000003749 cleanliness Effects 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 238000010792 warming Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- 229930192627 Naphthoquinone Natural products 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 239000012954 diazonium Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-O diazynium Chemical compound [NH+]#N IJGRMHOSHXDMSA-UHFFFAOYSA-O 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 150000002791 naphthoquinones Chemical class 0.000 claims 1
- 239000010410 layer Substances 0.000 description 27
- 239000002904 solvent Substances 0.000 description 6
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 229920002521 macromolecule Polymers 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000000608 laser ablation Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000009738 saturating Methods 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
- H01L31/09—Devices sensitive to infrared, visible or ultraviolet radiation
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0071—Active shielding
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
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- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Electromagnetism (AREA)
- General Physics & Mathematics (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Laminated Bodies (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a kind of graphene-based infra-red electromagnetic shielding filter, zinc sulphide window and preparation method thereof, preparation method comprises the following steps：In copper foil surface growth graphene film Gr；In graphene film side spray on polymer transition zone TL, copper foil/Gr/TL complexs are obtained after solidification；In polymeric transition layer side spraying liquid PMMA；Copper foil is etched away；Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface；Polymeric transition layer is dissolved, PMMA carriers separate with graphene film, obtain ZnS/Gr complexs；Until the electrical property of the graphene film of zinc sulphide window inner side meets electromagnetic shielding requirements, finally graphene-based infra-red electromagnetic shielding filter is formed on zinc sulphide window inner side surface.Infrared transmittivity of the present invention is high, easily prepared.
Description
Technical field
The present invention relates to electromangnetic spectrum field, more particularly to a kind of graphene-based infra-red electromagnetic shielding filter,
Zinc sulphide window and preparation method thereof.
Background technology
In modern military application, generally work(need to be prepared in zinc sulphide (ZnS) window inner surface of infrared acquisition, guidance system
Energy structure, makes window device on the premise of operation wavelength (8~12 μm) infrared waves high transmittance is ensured, to microwave region electromagnetism
Ripple has certain shielding action, and to realize system electromagnetism interference and reduce radar reflection section function, the functional structure is led to
It is commonly referred to as infra-red electromagnetic shielding filter.
Currently, can the saturating infra-red electromagnetic shielding filter of practical application be laser ablation metallic mesh on ZnS windows, its
The contradiction that special structure type has effectively reconciled between infrared light and high conductivity, but itself is still answered with technical process
It is miscellaneous, cost is high, transmitance is relatively low and the defects of Moire fringe.
The content of the invention
In view of this, the embodiment of the present invention provides a kind of graphene-based infra-red electromagnetic shielding filter and its preparation side
Method, main purpose are to improve infrared transmittivity.
To reach above-mentioned purpose, present invention generally provides following technical scheme：
In a first aspect, the embodiments of the invention provide a kind of preparation side of graphene-based infra-red electromagnetic shielding filter
Method, comprise the following steps：
Graphene film Gr is grown in copper foil surface, obtains copper foil/Gr complexs；
In the graphene film side spray on polymer transition zone TL of copper foil/Gr complexs, copper foil/Gr/ is obtained after solidification
TL complexs；
The polymeric transition layer side spraying liquid PMMA (polymethyl methacrylate) of copper foil/Gr/TL structures, after solidification
Obtain copper foil/Gr/TL/PMMA complexs；
Copper foil is etched away to obtain Gr/TL/PMMA complexs；
Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface, obtain obtaining ZnS/Gr/TL/PMMA complexs；
ZnS/Gr/TL/PMMA complexs are placed in organic solvent, dissolve polymeric transition layer, PMMA carriers and stone
Black alkene thin film separation, obtains ZnS/Gr complexs；
An at least layer graphene film is shifted in zinc sulphide window inner side by above-mentioned steps, until zinc sulphide window inner side
The electrical property of graphene film meets electromagnetic shielding requirements, is finally formed on zinc sulphide window inner side surface graphene-based infrared
Magnetic shielding filter.
Preferably, the copper foil-clad on quartz ampoule, carries out graphene film growth, the copper foil in tube furnace
Thickness is 25~125 μm.
Preferably, the copper foil-clad is placed in tube furnace on quartz ampoule and first pre-processed, stone is then carried out again
Black alkene film growth, the pretreatment are to be passed through high-purity H with 6~11sccmm flow velocity2, air pressure is maintained at 20~30Pa in stove,
And 1000 DEG C are warming up to 5~15 DEG C/s speed, it is incubated 10~30min.
Preferably, graphene film growth step is as follows：High-purity CH is passed through in tube furnace4, air pressure is 200 in holding furnace
~230Pa, 10~20min is reacted under 950~1100 DEG C of high temperature, react and room is cooled to 5~15 DEG C/s speed after terminating
Temperature, i.e., graphene film is grown in copper foil surface, obtain copper foil/Gr complexs.
Preferably, the thickness of the polymeric transition layer is 10~15 μm.
Preferably, the raw material of the polymeric transition layer is diluted to obtain by positive photoresist with solvent.
Preferably, the solvent is isopropanol.
Preferably, the volume ratio of the positive photoresist and the solvent is 1：1.
Preferably, the positive photoresist is AZ4620 photoresists.
Preferably, the composition of the positive photoresist is as follows：Phenolic resin and diazo naphthoquinone in mass ratio 1：1 mixing,
BTA is added as tackifier by the 3~11% of phenolic resin and diazo naphthoquinone gross mass.
Preferably, during etching copper foil, it is 0.02~0.07g/ml's that copper foil/Gr/TL/PMMA complexs are placed in into concentration
FeCl3Or Fe (NO3)3In solution etch 12~20h, after copper foil etches away completely remove Gr/TL/PMMA complexs, spend from
Sub- water cleans remaining etching liquid.
Preferably, when Gr/TL/PMMA complexs are transferred into zinc sulphide window inner surface, in the zinc sulphide window
Surface keep can plated film cleanliness factor, the zinc sulphide window sequentially using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol wipe
Wipe, being reached to zinc sulphide window inner surface can plated film cleanliness factor.
Preferably, polymeric transition layer is set quickly to dissolve using acetone organic solvent.
Second aspect, the embodiments of the invention provide a kind of graphene-based infra-red electromagnetic shielding filter, by above-mentioned reality
The method for applying example is prepared.
The third aspect, the embodiments of the invention provide a kind of zinc sulphide window, including wave filter, the wave filter is above-mentioned
Graphene-based infra-red electromagnetic shielding filter described in embodiment.
Compared with prior art, the beneficial effects of the present invention are：
The wave filter of the embodiment of the present invention has that manufacture craft is simple compared to metallic mesh structure, low manufacture cost
Feature；And small in 8~12 μm of service band light absorbs, transmitance is high.The wave filter of the embodiment of the present invention uses graphene
Film, no Moire fringe phenomenon, the signal/noise ratio of optical system is enhanced, can effectively suppress transmission function decay.
Brief description of the drawings
Fig. 1 is ZnS windows background and prepared infrared after individual layer, the saturating infra-red electromagnetic shielding filter of three layer graphene bases
Cross rate curve map.
Embodiment
The present invention is described in further detail with reference to specific embodiment, but it is not as a limitation of the invention.
In the description below, what different " embodiment " or " embodiment " referred to is not necessarily the same embodiment.In addition, one or more are implemented
Special characteristic, structure or feature in example can be combined by any suitable form.
The embodiments of the invention provide a kind of preparation method of graphene-based infra-red electromagnetic shielding filter, including it is as follows
Step：
Graphene film Gr is grown in copper foil surface, obtains copper foil/Gr complexs；
In the graphene film side spray on polymer transition zone TL of copper foil/Gr complexs, copper foil/Gr/ is obtained after solidification
TL complexs；
The polymeric transition layer side spraying liquid PMMA (polymethyl methacrylate) of copper foil/Gr/TL " structures, solidification
Copper foil/Gr/TL/PMMA complexs are obtained afterwards；
Copper foil is etched away to obtain Gr/TL/PMMA complexs；
Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface, obtain obtaining ZnS/Gr/TL/PMMA complexs；
ZnS/Gr/TL/PMMA complexs are placed in organic solvent, dissolve polymeric transition layer, PMMA carriers and stone
Black alkene thin film separation, obtains ZnS/Gr complexs；
An at least layer graphene film is shifted in zinc sulphide window inner side by above-mentioned steps, until zinc sulphide window inner side
The electrical property of graphene film meets electromagnetic shielding requirements, is finally formed on zinc sulphide window inner side surface graphene-based infrared
Magnetic shielding filter.
The wave filter of the embodiment of the present invention uses graphene film, has superhigh current carrying transport factor, extremely low absorptivity
And the physical characteristic such as extremely strong mechanical property.The carrier mobility of superelevation makes it to be obtained under relatively low carrier concentration level
The electrical conductivity of metallic mesh must be better than, show higher electromagnet shield effect.Meanwhile low carrier concentration can make graphene thin
The plasma wavelength red shift of film, effectively increase optical transmittance of the graphene film in infrared band.In addition, graphene is thin
Film sheet is as two-dimentional homogeneous material, in the absence of the caused Moire fringe phenomenon by optical interference.And manufacture craft is simple, system
Make the characteristics of cost is low；Small in 8~12 μm of service band light absorbs, transmitance is high.
The purity for the material being related in the embodiment of the present invention meets concerned countries standard.If hydrogen is high-purity hydrogen, copper foil
For high-purity copper foil.
The concrete technology that graphene film grows on copper foil can in terms of existing in selected.It is given below a kind of excellent
Select selective.In the embodiment of the present invention, copper foil-clad carries out graphene film growth, copper foil on quartz ampoule in tube furnace
Thickness is 25~125 μm.And pretreatment is first carried out to copper foil contributes to the growth of graphene film.Therefore, the present invention is implemented
In example, copper foil-clad is placed in tube furnace on quartz ampoule and first pre-processed, and then carries out graphene film growth again, pre- place
Manage bar part is as follows：High-purity H is passed through with 6~11sccmm flow velocity2, air pressure is maintained at 20~30Pa in stove, and with 5~15 DEG C/s
Speed be warming up to 1000 DEG C, be incubated 10~30min.Graphene film growth step is as follows：High-purity CH is passed through in tube furnace4,
Air pressure is 200~230Pa in holding furnace, and 10~20min is reacted under 950~1100 DEG C of high temperature, is reacted after terminating with 5~15
DEG C/s speed is cooled to room temperature, i.e., graphene film is grown in copper foil surface, obtain copper foil/Gr complexs.The present invention is implemented
In example, the spray on polymer transition zone TL between the graphene film and PMMA carriers of copper foil/Gr complexs, accelerate follow-up
The separation time of PMMA carriers and graphene film.When PMMA carriers are painted on into graphene film side, follow-up is de-
24 hours are needed from the time, due to long period and organic solvent exposure, adds the risk of graphene film fault of construction.And
In the embodiment of the present invention, between graphene film and PMMA carriers after spray on polymer transition zone TL, in follow-up disengaging
Journey only needs 12-13 hours, reduces graphene film fault of construction.The thickness of polymeric transition layer is 10~15 μm, the present embodiment
In polymeric transition layer raw material diluted by positive photoresist after obtain, and the dilution ratio of positive photoresist and solvent can root
According to it needs to be determined that.General positive photoresist and solvent by volume 1：1 or so dilution can obtain required viscosity.And positivity light
The main composition of photoresist is preferably phenolic resin and diazo naphthoquinone, such as AZ4620 photoresists.A kind of positive photoresist is given below
Preferred optimum ratio for reference.Phenolic resin and diazo naphthoquinone are 1 in mass ratio：1 mixing, by phenolic resin and diazo naphthoquinone
The 3~11% of mixture gross mass add the BTA as tackifier.Solvent preferably uses isopropanol.The macromolecule mistake
Cross layer and be highly soluble in organic solvent, effectively reduce the time for dissolving away macromolecule carrier, reduce graphene film fault of construction.Using
Concentration is (0.02~0.07) g/ml FeCl3Or Fe (NO3)3Solution etches 12~20h of copper foil, after copper foil etches away completely
Gr/TL/PMMA complexs are removed, net remaining etching liquid is washed with deionized water.Gr/TL/PMMA complexs are transferred to zinc sulphide
During window inner surface, zinc sulphide window inner surface is kept can plated film cleanliness factor.It specifically can sequentially use petroleum ether, ethanol-second
Ether mixed liquor, absolute ethyl alcohol wipe zinc sulphide window, and being reached to zinc sulphide window inner surface can plated film cleanliness factor.Dissolve macromolecule mistake
Crossing the organic solvent of layer can choose in known organic solvent.Such as acetone.
The above method of the embodiment of the present invention can obtain graphene-based infra-red electromagnetic shielding filter, and have the filter
The zinc sulphide window of ripple device.
Below by specific embodiment, the present invention will be further described.
Embodiment 1：
(1) the high-purity copper foil of 50 μ m-thicks is wrapped on quartz ampoule and be placed in tube furnace, with 8sccmm flow velocity in stove
It is passed through high-purity H2, air pressure is 25Pa in adjusting air valve holding furnace, and is warming up to 1000 DEG C with 10 DEG C/s speed, is incubated 15min；
(2) high-purity CH is passed through into tube furnace4, air pressure is 200Pa in holding furnace, reacts 20min under 1050 DEG C of high temperature.
React and room temperature is cooled to 10 DEG C/s speed after terminating, obtain copper foil/Gr complexs；
(3) the macromolecule mistake for being 12 μm in the graphene film side coating thickness of copper foil/Gr complexs using glue spreader
A layer TL (transition layer) is crossed, copper foil/Gr/TL complexs are obtained after solidification；The composition of polymeric transition layer is as follows：Phenol
Urea formaldehyde and diazo naphthoquinone are 1 in mass ratio：1 mixing, benzene is added by the 4% of phenolic resin and diazo naphthoquinone mixture gross mass
And triazole, photoresist is obtained, photoresist presses 1 with isopropanol：1 volume ratio dilution；
(4) liquid PMMA is sprayed into the polymeric transition layer side of copper foil/Gr/TL complexs using glue spreader, solidified
Copper foil/Gr/TL/PMMA complexs are obtained afterwards；
(5) copper foil/Gr/TL/PMMA complexs are placed in the FeCl that concentration is 0.03g/ml314h is etched in solution, treats copper
Paper tinsel removes Gr/TL/PMMA complexs after etching away completely, and net remaining etching liquid is washed with deionized water；
(6) sequentially zinc sulphide window inner surface is wiped to can using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol
Plated film cleanliness factor；
(7) Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface, obtain ZnS/Gr/TL/PMMA complexs；
(8) ZnS/Gr/TL/PMMA complexs are placed in acetone, polymeric transition layer is quickly dissolved, dissolution time is
12 hours, PMMA carriers separated with graphene film, take out " ZnS/Gr " structure and processing is dried.
Embodiment 2：
(1) the high-purity copper foil of 50 μ m-thicks is wrapped on quartz ampoule and be placed in tube furnace.With 8sccmm flow velocity in stove
It is passed through high-purity H2, air pressure is 25Pa in adjusting air valve holding furnace, and is warming up to 1000 DEG C with 10 DEG C/s speed, is incubated 15min；
(2) high-purity CH is passed through into tube furnace4, air pressure is 200Pa in holding furnace, reacts 20min under 1050 DEG C of high temperature.
React and room temperature is cooled to 10 DEG C/s speed after terminating, obtain copper foil/Gr complexs；
(3) using glue spreader in the polymeric transition that copper foil/Gr complex graphene films side coating thickness is 12 μm
Layer, copper foil/Gr/TL complexs are obtained after solidification；The composition of polymeric transition layer is as follows：Phenolic resin and diazo naphthoquinone press quality
Than for 1：1 mixing, BTA is added by the 10% of phenolic resin and diazo naphthoquinone mixture gross mass, obtains photoresist,
Photoresist presses 1 with isopropanol：1 volume ratio dilution；
(4) liquid PMMA is sprayed into the polymeric transition layer side of copper foil/Gr/TL complexs using glue spreader, solidified
Copper foil/Gr/TL/PMMA complexs are obtained afterwards；
(5) copper foil/Gr/TL/PMMA complexs are placed in the Fe (NO that concentration is 0.03g/ml3)314h is etched in solution.Treat
Copper foil removes Gr/TL/PMMA complexs after etching away completely, and net remaining etching liquid is washed with deionized water；
(6) sequentially zinc sulphide window inner surface is wiped to can using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol
Plated film cleanliness factor；
(7) Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface, obtain ZnS/Gr/TL/PMMA complexs；
(8) ZnS/Gr/TL/PMMA complexs are placed in acetone, polymeric transition layer is quickly dissolved, dissolution time is
12 hours, PMMA carriers separated with graphene film, take out ZnS/Gr complexs and processing is dried, keep graphene film table
Clean in face；
(9) repeat step (3)~(5), the middle operation in (7)~(8) 3 times, obtain graphene-based infra-red electromagnetic mask filter
Device.
Fig. 1 is zinc sulphide window background (reactive filter) and (three layers of embodiment 1 (single-layer graphene film) and embodiment 2
Graphene film) infrared transmittivity curve map.As can be seen from the figure compared with zinc sulphide window background, the list of embodiment 1
The decay of layer graphene film filter and three layer graphene film filters of embodiment 2 to 8~12 μm of infrared waveses is only
1% and 3.2%, and decay of the existing laser ablation metallic mesh to 8~12 μm of infrared waveses is up to 15%~20%.It can be seen that
The graphene-based infra-red electromagnetic shielding filter of the embodiment of the present invention is thoroughly red with existing laser ablation metallic mesh is much better than
The Infrared grey image of outer magnetic shielding filter.
The foregoing is only a specific embodiment of the invention, but protection scope of the present invention is not limited thereto, any
Those familiar with the art the invention discloses technical scope in, change or replacement can be readily occurred in, should all be contained
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be based on the protection scope of the described claims.
Claims (10)
1. the preparation method of graphene-based infra-red electromagnetic shielding filter, it is characterised in that comprise the following steps：
Graphene film Gr is grown in copper foil surface, obtains copper foil/Gr complexs；
In the graphene film side spray on polymer transition zone TL of copper foil/Gr complexs, it is multiple that copper foil/Gr/TL is obtained after solidification
It is fit；
The polymeric transition layer side spraying liquid PMMA of copper foil/Gr/TL complexs, obtains copper foil/Gr/TL/PMMA after solidification
Complex；
Copper foil is etched away to obtain Gr/TL/PMMA complexs；
Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface, obtain obtaining ZnS/Gr/TL/PMMA complexs；
ZnS/Gr/TL/PMMA complexs are placed in organic solvent, dissolve polymeric transition layer, PMMA carriers and graphene
Thin film separation, obtain ZnS/Gr complexs；
An at least layer graphene film is shifted in zinc sulphide window inner side by above-mentioned steps, until the graphite of zinc sulphide window inner side
The electrical property of alkene film meets electromagnetic shielding requirements, finally forms graphene-based infra-red electromagnetic on zinc sulphide window inner side surface
Shielding filter.
2. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that institute
Copper foil-clad is stated on quartz ampoule, graphene film growth is carried out in tube furnace, the copper thickness is 25~125 μm.
3. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that institute
State copper foil-clad and be placed on quartz ampoule in tube furnace and first pre-processed, then carry out graphene film growth again, it is described pre-
Handle to be passed through high-purity H with 6~11sccmm flow velocity2, air pressure is maintained at 20~30Pa in stove, and with 5~15 DEG C/s speed
1000 DEG C are warming up to, is incubated 10~30min.
4. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that stone
Black alkene thin film growth step is as follows：High-purity CH is passed through in tube furnace4, air pressure is 200~230Pa in holding furnace, 950~1100
React 10~20min under DEG C high temperature, reaction with 5~15 DEG C/s speed is cooled to room temperature after terminating, i.e., is grown in copper foil surface
Graphene film, obtain copper foil/Gr complexs.
5. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that institute
The thickness for stating polymeric transition layer is 10~15 μm；The polymeric transition layer is obtained by positive photoresist with isopropanol；
The composition composition of the positive photoresist is as follows：The mass ratio of phenolic resin and diazo naphthoquinone is 1：1, by phenolic resin and diazonium
The 3~11% of naphthoquinones gross mass add BTA；The volume ratio of the positive photoresist and isopropanol is 1：1.
6. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that carve
When losing copper foil, copper foil/Gr/TL/PMMA complexs are placed in the FeCl that concentration is 0.02~0.07g/ml3Or Fe (NO3)3Solution
12~20h of middle etching, Gr/TL/PMMA complexs are removed after copper foil etches away completely, net remaining etching is washed with deionized water
Liquid.
7. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that will
When Gr/TL/PMMA complexs are transferred to zinc sulphide window inner surface, the zinc sulphide window inner surface is kept can plated film cleaning
Degree, the zinc sulphide window sequentially using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol wipe, to zinc sulphide window in table
Face reaches can plated film cleanliness factor.
8. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that adopt
Polymeric transition layer is set quickly to dissolve with acetone organic solvent.
9. graphene-based infra-red electromagnetic shielding filter, it is characterised in that as the method system described in claim any one of 1-8
It is standby to obtain.
10. zinc sulphide window, including wave filter, it is characterised in that the wave filter is graphene-based described in claim 9
Infra-red electromagnetic shielding filter.
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| CN107144899B (en) * | 2017-06-29 | 2023-04-18 | 中国建筑材料科学研究总院 | Chalcogenide optical element with electromagnetic shielding performance and preparation method thereof |
| CN107266841A (en) * | 2017-07-19 | 2017-10-20 | 冯苇荣 | Acrylic functional graphene integration filtering IC and preparation method thereof |
| CN107266861A (en) * | 2017-07-19 | 2017-10-20 | 冯苇荣 | Epoxy resin functional graphene integration filtering IC and preparation method thereof |
| CN107266842A (en) * | 2017-07-19 | 2017-10-20 | 冯苇荣 | Polynary inserts functional graphene integration filtering IC and preparation method thereof |
| CN110787971B (en) * | 2019-11-28 | 2022-06-14 | 江西邦力达科技股份有限公司 | High-heat-conduction near-infrared electromagnetic shielding film |
| CN113504588B (en) * | 2021-07-06 | 2022-09-13 | 西安工业大学 | Preparation method of electromagnetic shielding compatible infrared anti-reflection film device |
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