CN106653931A - Graphene-based infrared transmission electromagnetic shielding filter, zinc sulfide window and fabrication method of graphene-based infrared transmission electromagnetic shielding filter - Google Patents
Graphene-based infrared transmission electromagnetic shielding filter, zinc sulfide window and fabrication method of graphene-based infrared transmission electromagnetic shielding filter Download PDFInfo
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- CN106653931A CN106653931A CN201611224658.6A CN201611224658A CN106653931A CN 106653931 A CN106653931 A CN 106653931A CN 201611224658 A CN201611224658 A CN 201611224658A CN 106653931 A CN106653931 A CN 106653931A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 79
- 239000005083 Zinc sulfide Substances 0.000 title claims abstract description 54
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 12
- 230000005540 biological transmission Effects 0.000 title abstract description 8
- 238000004519 manufacturing process Methods 0.000 title abstract description 6
- 229910052984 zinc sulfide Inorganic materials 0.000 title abstract 4
- 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 57
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims abstract description 55
- 239000004926 polymethyl methacrylate Substances 0.000 claims abstract description 55
- 230000007704 transition Effects 0.000 claims abstract description 30
- 238000005530 etching Methods 0.000 claims abstract description 10
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010409 thin film Substances 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 54
- 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
- 238000002360 preparation method Methods 0.000 claims description 13
- 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
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical group CC(C)O KFZMGEQAYNKOFK-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
- 239000007788 liquid Substances 0.000 claims description 10
- 239000005011 phenolic resin Substances 0.000 claims description 10
- 229920001568 phenolic resin Polymers 0.000 claims description 10
- 239000000969 carrier Substances 0.000 claims description 9
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 239000003708 ampul 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
- 238000007711 solidification Methods 0.000 claims description 8
- 230000008023 solidification Effects 0.000 claims description 8
- 230000003749 cleanliness Effects 0.000 claims description 7
- 238000010790 dilution Methods 0.000 claims description 7
- 239000012895 dilution Substances 0.000 claims description 7
- 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
- 229920000642 polymer Polymers 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 239000007921 spray Substances 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
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims 2
- 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
- 230000003628 erosive effect Effects 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000010792 warming Methods 0.000 claims 1
- 229920002521 macromolecule Polymers 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract 3
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 abstract 2
- 239000010410 layer Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 7
- 238000007792 addition Methods 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000008569 process Effects 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
- 230000003287 optical effect Effects 0.000 description 3
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 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
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 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
- 230000035699 permeability Effects 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
- 238000002834 transmittance Methods 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- 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 graphene-based infrared transmission electromagnetic shielding filter, a zinc sulfide window and a fabrication method of the graphene-based infrared transmission electromagnetic shielding filter. The fabrication method comprises the following steps of growing a graphene thin film Gr on a surface of a copper foil; spraying a macromolecule transition layer TL at one side of the graphene thin film, and obtaining a copper coil/Gr/TL composite body after curing; spraying a liquid-state polymethyl methacrylate (PMMA) at one side of the macromolecule transition layer; etching the copper foil; transferring a Gr/TL/PMMA composite body to an inner surface of the zinc sulfide window; and dissolving the macromolecule transition layer, and separating a PMMA carrier from the graphene thin film to obtain a ZnS/Gr composite body until the electrical performance of the graphene thin film at an inner side of the zinc sulfur window conforms to the electromagnetic shielding requirement and the graphene-based infrared transmission electromagnetic shielding filter is finally formed on the surface of the inner side of the zinc sulfur window. The graphene-based infrared transmission electromagnetic shielding filter is high in infrared transmission and is easy to fabricate.
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) the 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 permeability 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 version has effectively reconciled between infrared light and high conductivity, but itself is still multiple with technical process
Miscellaneous, high cost, transmitance be relatively low and the defect such as 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 is to improve infrared transmittivity.
To reach above-mentioned purpose, present invention generally provides following technical scheme：
In a first aspect, embodiments providing a kind of preparation side of graphene-based infra-red electromagnetic shielding filter
Method, comprises the steps：
Graphene film Gr is grown in copper foil surface, Copper Foil/Gr complexs are obtained；
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；
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 and obtains Gr/TL/PMMA complexs；
Gr/TL/PMMA complexs are transferred to into zinc sulphide window inner surface, ZnS/Gr/TL/PMMA complexs are obtained obtaining；
ZnS/Gr/TL/PMMA complexs are placed in organic solvent, the dissolving of polymeric transition layer, PMMA carriers and stone is made
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, finally forms graphene-based infrared on zinc sulphide window inner side surface
Magnetic shielding filter.
Preferably, the copper foil-clad is on quartz ampoule, graphene film growth, the Copper Foil are carried out in tube furnace
Thickness is 25～125 μm.
Preferably, the copper foil-clad is placed in tube furnace on quartz ampoule first being pre-processed, stone is then carried out again
Black alkene film growth, the pretreatment is to be passed through high-purity H with the flow velocity of 6～11sccmm2, air pressure is maintained at 20～30Pa in stove,
And with the ramp of 5～15 DEG C/s to 1000 DEG C, 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, reacts 10～20min under 950～1100 DEG C of high temperature, and reaction is cooled to room after terminating with the speed of 5～15 DEG C/s
Temperature, i.e., grow graphene film in copper foil surface, obtains 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 obtained by the dilution of positive photoresist solvent.
Preferably, the solvent is isopropanol.
Preferably, the positive photoresist is 1 with the volume ratio of the solvent：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,
By 3～11% addition BTAs of phenolic resin and diazo naphthoquinone gross mass as tackifier.
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 is etched away completely remove Gr/TL/PMMA complexs, spend from
Sub- water cleans remnants etching liquids.
Preferably, when Gr/TL/PMMA complexs are transferred to 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, reaching to zinc sulphide window inner surface can plated film cleanliness factor.
Preferably, making polymeric transition layer quickly dissolve using acetone organic solvent.
Second aspect, embodiments provides a kind of graphene-based infra-red electromagnetic shielding filter, by above-mentioned reality
The method for applying example is prepared.
The third aspect, embodiments provides a kind of zinc sulphide window, including wave filter, and 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 is：
The wave filter of the embodiment of the present invention is simple with manufacture craft compared to metallic mesh structure, low manufacture cost
Feature；And little in 8～12 μm of service band light absorbs, transmitance is high.The wave filter of the embodiment of the present invention adopts Graphene
Film, without Moire fringe phenomenon, enhances the signal/noise ratio of optical system, can effectively suppress transmission function decay.
Description of the drawings
Fig. 1 is ZnS windows background and prepares infrared after individual layer, the saturating infra-red electromagnetic shielding filter of three layer graphene bases
Cross rate curve map.
Specific 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 " embodiments " or " embodiment " referred to is not necessarily same embodiment.Additionally, one or more enforcements
Special characteristic, structure or feature in example can be combined by any suitable form.
A kind of preparation method of graphene-based infra-red electromagnetic shielding filter is embodiments provided, including it is as follows
Step：
Graphene film Gr is grown in copper foil surface, Copper Foil/Gr complexs are obtained；
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；
Polymeric transition layer side spraying liquid PMMA (polymethyl methacrylate) of Copper Foil/Gr/TL " structure, solidification
Copper Foil/Gr/TL/PMMA complexs are obtained afterwards；
Copper Foil is etched away and obtains Gr/TL/PMMA complexs；
Gr/TL/PMMA complexs are transferred to into zinc sulphide window inner surface, ZnS/Gr/TL/PMMA complexs are obtained obtaining；
ZnS/Gr/TL/PMMA complexs are placed in organic solvent, the dissolving of polymeric transition layer, PMMA carriers and stone is made
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, finally forms graphene-based infrared on zinc sulphide window inner side surface
Magnetic shielding filter.
The wave filter of the embodiment of the present invention adopts graphene film, with superhigh current carrying transport factor, extremely low absorptivity
And the physical characteristic such as extremely strong mechanical property.The carrier mobility of superelevation is obtained by making it under relatively low carrier concentration level
The electrical conductivity of metallic mesh must be better than, higher electromagnet shield effect is shown.Meanwhile, low carrier concentration can make Graphene thin
The plasma wavelength red shift of film, effectively increases optical transmittance of the graphene film in infrared band.Additionally, Graphene is thin
There is no the Moire fringe phenomenon produced by optical interference as two-dimentional homogeneous material in film sheet.And manufacture craft is simple, system
The characteristics of making low cost；Little in 8～12 μm of service band light absorbs, transmitance is high.
The purity of the material being related in the embodiment of the present invention meets concerned countries standard.As hydrogen be high-purity hydrogen, Copper Foil
For high-purity Copper Foil.
The concrete technology that graphene film is grown on the 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 first Copper Foil is carried out to pre-process the growth for contributing to graphene film.Therefore, the present invention is implemented
In example, copper foil-clad is placed in tube furnace on quartz ampoule and is first pre-processed, and graphene film growth is then carried out again, pre- place
Manage bar part is as follows：High-purity H is passed through with the flow velocity of 6～11sccmm2, air pressure is maintained at 20～30Pa in stove, and with 5～15 DEG C/s
Ramp 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/speed of s is cooled to room temperature, i.e., grow graphene film in copper foil surface, obtains 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 is accelerated 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, the risk of graphene film fault of construction is increased.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 by obtaining after positive photoresist dilution, 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 is obtained 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
BTA of 3～11% additions of mixture gross mass as tackifier.Solvent preferably adopts 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 the FeCl of (0.02～0.07) g/ml3Or Fe (NO3)3Solution etches 12～20h of Copper Foil, after Copper Foil is etched away completely
Gr/TL/PMMA complexs are removed, deionized water cleans remnants etching liquids.Gr/TL/PMMA complexs are transferred to into zinc sulphide
During window inner surface, zinc sulphide window inner surface keeps can plated film cleanliness factor.Specifically can sequentially use petroleum ether, ethanol-second
Ether mixed liquor, absolute ethyl alcohol wipe zinc sulphide window, and reaching to zinc sulphide window inner surface can plated film cleanliness factor.Dissolving macromolecule mistake
Crossing the organic solvent of layer can choose in known organic solvent.Such as acetone.
The said method of the embodiment of the present invention can obtain graphene-based infra-red electromagnetic shielding filter, and with 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 is placed in tube furnace, with the flow velocity of 8sccmm in stove
It is passed through high-purity H2, air pressure is 25Pa in adjusting air valve holding furnace, and with the ramp of 10 DEG C/s to 1000 DEG C, is incubated 15min；
(2) high-purity CH is passed through in tube furnace4, air pressure is 200Pa in holding furnace, and under 1050 DEG C of high temperature 20min is reacted.
Reaction is cooled to room temperature after terminating with the speed of 10 DEG C/s, obtains Copper Foil/Gr complexs；
(3) using glue spreader in the macromolecule mistake that the graphene film side coating thickness of Copper Foil/Gr complexs is 12 μm
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, by phenolic resin and 4% addition benzene of 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, is solidified
Copper Foil/Gr/TL/PMMA complexs are obtained afterwards；
(5) Copper Foil/Gr/TL/PMMA complexs are placed in into the FeCl that concentration is 0.03g/ml314h is etched in solution, copper is treated
Paper tinsel removes Gr/TL/PMMA complexs after etching away completely, deionized water cleans remnants etching liquids；
(6) sequentially using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol zinc sulphide window inner surface is wiped to can
Plated film cleanliness factor；
(7) Gr/TL/PMMA complexs are transferred to into 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 were separated with graphene film, were taken out " ZnS/Gr " structure and were dried process.
Embodiment 2：
(1) the high-purity Copper Foil of 50 μ m-thicks is wrapped on quartz ampoule and is placed in tube furnace.With the flow velocity of 8sccmm in stove
It is passed through high-purity H2, air pressure is 25Pa in adjusting air valve holding furnace, and with the ramp of 10 DEG C/s to 1000 DEG C, is incubated 15min；
(2) high-purity CH is passed through in tube furnace4, air pressure is 200Pa in holding furnace, and under 1050 DEG C of high temperature 20min is reacted.
Reaction is cooled to room temperature after terminating with the speed of 10 DEG C/s, obtains 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, obtains Copper Foil/Gr/TL complexs after solidification；The composition of polymeric transition layer is as follows：Phenolic resin and diazo naphthoquinone press quality
Than for 1：1 mixing, by phenolic resin and 10% addition BTA of 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, is solidified
Copper Foil/Gr/TL/PMMA complexs are obtained afterwards；
(5) Copper Foil/Gr/TL/PMMA complexs are placed in into 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, deionized water cleans remnants etching liquids；
(6) sequentially using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol zinc sulphide window inner surface is wiped to can
Plated film cleanliness factor；
(7) Gr/TL/PMMA complexs are transferred to into 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 were separated with graphene film, were taken out ZnS/Gr complexs and were dried process, kept graphene film table
Clean in face；
(9) operation 3 times in repeat step (3)～(5), (7)～(8), 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
Decay of the three layer graphene film filters of layer graphene film filter and embodiment 2 to 8～12 μm of infrared waveses be only
1% and 3.2%, and existing laser ablation metallic mesh to the decay of 8～12 μm of infrared waveses 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 above, the only specific embodiment of the present 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, all should contain
Cover within protection scope of the present invention.Therefore, protection scope of the present invention should be defined by the scope of the claims.
Claims (10)
1. the preparation method of graphene-based infra-red electromagnetic shielding filter, it is characterised in that comprise the steps：
Graphene film Gr is grown in copper foil surface, Copper Foil/Gr complexs are obtained；
In the graphene film side spray on polymer transition zone TL of Copper Foil/Gr complexs, Copper Foil/Gr/TL is obtained after solidification multiple
It is fit；
Polymeric transition layer side spraying liquid PMMA of Copper Foil/Gr/TL structures, obtains Copper Foil/Gr/TL/PMMA multiple after solidification
It is fit；
Copper Foil is etched away and obtains Gr/TL/PMMA complexs；
Gr/TL/PMMA complexs are transferred to into zinc sulphide window inner surface, ZnS/Gr/TL/PMMA complexs are obtained obtaining；
ZnS/Gr/TL/PMMA complexs are placed in organic solvent, the dissolving of polymeric transition layer, PMMA carriers and Graphene is made
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 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, graphene film growth is then carried out again, it is described pre-
It is processed as being passed through high-purity H with the flow velocity of 6～11sccmm2, air pressure is maintained at 20～30Pa in stove, and with the speed of 5～15 DEG C/s
1000 DEG C are warming up to, 10～30min is incubated.
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
10～20min is reacted under DEG C high temperature, reaction is cooled to room temperature after terminating with the speed of 5～15 DEG C/s, i.e., grow in copper foil surface
Graphene film, obtains 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 the dilution of positive photoresist solvent；Institute
State the as follows into being grouped into of positive photoresist：The mass ratio of phenolic resin and diazo naphthoquinone is 1：1, by phenolic resin and diazonium naphthalene
3～11% addition BTAs of quinone gross mass；The solvent is isopropanol；The volume ratio of the positive photoresist and solvent
For 1：1.
6. the preparation method of graphene-based infra-red electromagnetic shielding filter according to claim 1, it is characterised in that carve
During erosion Copper Foil, Copper Foil/Gr/TL/PMMA complexs are placed in into the FeCl that concentration is 0.02～0.07g/ml3Or Fe (NO3)3Solution
12～20h of middle etching, removes Gr/TL/PMMA complexs after Copper Foil is etched away completely, and deionized water cleans remaining etching
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 keeps can plated film cleaning
Degree, the zinc sulphide window is sequentially wiped using petroleum ether, alcohol-ether mixed liquor, absolute ethyl alcohol, the table to zinc sulphide window
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 the method system by described in any one of claim 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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