CN107921402A - The perforated sheet of graphene-based material - Google Patents
The perforated sheet of graphene-based material Download PDFInfo
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- CN107921402A CN107921402A CN201680045785.1A CN201680045785A CN107921402A CN 107921402 A CN107921402 A CN 107921402A CN 201680045785 A CN201680045785 A CN 201680045785A CN 107921402 A CN107921402 A CN 107921402A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 379
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 239
- 239000000463 material Substances 0.000 title claims abstract description 172
- 239000002356 single layer Substances 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 40
- 239000011148 porous material Substances 0.000 claims abstract description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 87
- 229910002804 graphite Inorganic materials 0.000 claims description 64
- 239000010439 graphite Substances 0.000 claims description 64
- 229910052760 oxygen Inorganic materials 0.000 claims description 27
- 239000001301 oxygen Substances 0.000 claims description 27
- 239000010410 layer Substances 0.000 claims description 23
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000007789 gas Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 7
- 239000010949 copper Substances 0.000 claims description 7
- 230000007547 defect Effects 0.000 claims description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- -1 nitrogenous carbon compound Chemical class 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical class 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052756 noble gas Inorganic materials 0.000 claims description 3
- 230000005855 radiation Effects 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001336 alkenes Chemical class 0.000 claims 2
- 239000006185 dispersion Substances 0.000 claims 2
- 229910003481 amorphous carbon Inorganic materials 0.000 claims 1
- 150000002431 hydrogen Chemical group 0.000 claims 1
- CSJDCSCTVDEHRN-UHFFFAOYSA-N methane;molecular oxygen Chemical compound C.O=O CSJDCSCTVDEHRN-UHFFFAOYSA-N 0.000 claims 1
- 150000002500 ions Chemical class 0.000 description 63
- 239000000758 substrate Substances 0.000 description 17
- 238000012360 testing method Methods 0.000 description 14
- 238000005229 chemical vapour deposition Methods 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 230000005540 biological transmission Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 238000003917 TEM image Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000004080 punching Methods 0.000 description 4
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 230000014509 gene expression Effects 0.000 description 3
- 238000010884 ion-beam technique Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 2
- 230000005865 ionizing radiation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007858 starting material Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002837 carbocyclic group Chemical group 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 229910021386 carbon form Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
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- 238000001914 filtration Methods 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002285 radioactive effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/56—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0083—Thermal after-treatment
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- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
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- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/06—Flat membranes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
- B01D71/021—Carbon
- B01D71/0211—Graphene or derivates thereof
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/26—Deposition of carbon only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/04—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of carbon-silicon compounds, carbon or silicon
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- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
- B01D2325/02831—Pore size less than 1 nm
Abstract
Provide the perforated sheet of the graphene-based material with multiple perforation.The perforated sheet can include the single-layer graphene of perforation.The perforation can be located on the area more than 10% of the piece of the graphene-based material, and the average pore size of the perforation is selected from 0.3nm to 1 μm.Additionally provide the method for preparing the perforated sheet.
Description
Cross reference to related applications
The 62/201st of entitled " perforated sheet of graphene-based material " submitted for 5th this application claims August in 2015,
The 62/th of entitled " pierceable of graphene-based material " that No. 527 U.S. Provisional Applications and August in 2015 are submitted on the 5th
The benefit of priority of 201, No. 539 U.S. Provisional Applications, both contents of the provisional application are integrally incorporated this by quoting
Text.With the application at the same time, it is desirable to which another U.S. Patent application of the benefit of priority of identical two provisional applications is
With sequence number _ _/_ _ _ _ _ _ _ entitled " pierceable of graphene-based material " submitted, its content pass through quote it is overall
It is incorporated herein.
Background
In the various forms of graphene, graphene has obtained extensive concern in many applications, mainly by
In the favourable of the optical and electronic property of mechanical strength in its high conductivity value and high thermal conductivity value, excellent plane and uniqueness
Combination.It is proposed perforation graphene being used in filtration application.
In Liu et al. people, Nano Lett.2008, volume 8, the 7th phase, has been disclosed for by sudden and violent in the 1965-1970 pages
It is exposed to oxygen (O2) hole or perforation are formed in graphene.As described therein, using 350 support oxygen in 1 atmospheric pressure (atm) argon
Continue in gas at 500 DEG C 2 it is small when, 20nm is etched in single-layer graphene to the through hole or hole of 180nm scopes.It is reported that
It is by mechanically pulling off Kish preparing graphite alkene samples.
Kim et al. " Fabrication and Characterization of Large Area,
Semiconducting Nanoperforated Graphene Materials, " Nano Letters 2010 years volume 10,
4th phase, on March 1st, 2010, another method is described in the 1125-1131 pages.This reference describes that gathered using self assembly
Compound produces the mask for being adapted for use with reactive ion etching (RIE) and being patterned.P (S- block M MA) block copolymer
The array of P MMA row is formed, it forms the through hole for RIE when removing.It is reported that it is by mechanically pulling off to form graphite
Alkene.
General introduction
Some embodiments provide the piece of the perforated sheet including graphene-based material.Perforation can be located at graphene base material
Described of material is more than on 10% or the area more than 15%.In other embodiments, perforation field can correspond to
0.1% or bigger of the area of the piece of the graphene-based material.In a further embodiment, the average pore of perforation
Size can be selected from 0.3nm to 1 μm.At least one lateral dimension of described can be more than 1mm, more than 1cm or more than 3cm.
Some embodiments provide the perforated sheet of graphene-based material, and the graphene-based material is included before perforation
Single-layer graphene, the perforated sheet of graphene-based material include multiple perforation, it is characterised in that the perforation can be located at the stone
The piece of mertenyl material more than 10% the area on and perforate average pore size can be selected from 0.3nm to 1 μm.
In some embodiments, the perforated sheet of graphene-based material includes the perforation single-layer graphene with multiple perforation, described to wear
Hole is characterized in that what perforation can be located on the area more than 10% of the piece of the graphene-based material and perforate
Average pore size can be selected from 0.3nm to 1 μm.
In some embodiments, the coefficient of variation of pore-size can be 0.1 to 2,0.5 to 2 or 0.1 to 0.5.Another
In some outer embodiments, the average pore size of perforation can be 0.3nm to 0.1 μm or 0.3nm to 1 μm.
In some embodiments, the piece of the graphene-based material before perforating include with surface single-layer graphene and
Non-graphite olefinic carbon sill on the single-layer graphene is provided.In some embodiments, single-layer graphene can have
At least two surfaces, such as substrate side surface and the Free Surface for forming apparent surface.For example, non-graphite olefinic carbon sill can be with
There is provided on one or two surface of single-layer graphene.In some embodiments, the piece of graphene-based material includes individual layer
Or multi-layer graphene or the piece of its combination.
In some embodiments, can be carried out by chemical vapor deposition (CVD) and then before perforation at least one
In addition adjusting or processing step, form the piece of graphene-based material.In some embodiments, adjusting method as described herein
The degree on non-graphite olefinic carbon sill covering single-layer graphene surface can be reduced, the non-graphite olefinic carbon sill can be reduced
Mobility, and can reduce the non-graphite olefinic carbon sill volatility and/or its combination.
In some embodiments, non-graphite olefinic carbon sill includes at least 80% carbon or 20% to 100% carbon.In addition
Some embodiments in, the non-graphite olefinic carbon sill further includes non-carbon element.In some embodiments, the non-carbon
Element can be selected from hydrogen, oxygen, silicon, copper, iron and combinations thereof.In some embodiments, the non-graphite olefinic carbon sill has
Element composition comprising carbon, hydrogen and oxygen.In a further embodiment, the non-graphite olefinic carbon sill, which can have, includes nothing
The molecular composition of setting carbon, one or more hydrocarbons or any combination of these.In some other embodiments,
Non-carbon element (such as boron or silicon) can substitute the carbon in lattice.In some embodiments, the non-graphite olefinic carbon sill
It can not show long-range order.In some embodiments, non-graphite olefinic carbon sill can be with the single-layer graphene
The surface physics contact.In some embodiments, being measured after the characteristic of non-graphite olefinic carbon material such as perforation
Characteristic.
After perforation, the perforated sheet of graphene-based material can keep single-layer graphene or existing for before perforation
Single-layer graphene can become substantially unordered.In some embodiments, the feature of the single-layer graphene can be greatly
In or equal to 1 micron (1 μm) long-range order average-size domain.In some other embodiments, the individual layer
Graphene can have the unordered degree for the long-range lattice period for being characterized in that 1 micron of order of magnitude.In some other implementations
In scheme, the single-layer graphene has the unordered degree for being characterized in that the lattice defect less than 1% content.In some embodiment party
In case, the lattice of single-layer graphene can be destroyed in the scale of 1nm to 10nm.In some other embodiments,
The perforated sheet of graphene-based material can not show long-range order.In some embodiments, the perforation of graphene-based material
Unordered feature in piece can be 6 feature point diffractions for lacking graphene, it characterizes the sky of falling lattice of ordered graphene
Between (reciprocal lattice space).
In some embodiments, there is provided the method for preparing the perforated sheet of graphene-based material.For example, some embodiment party
Case provides the method perforated to the piece of graphene-based material, the described method includes：The piece of the graphene-based material is provided, it is described
Graphene-based material includes the single-layer graphene with surface；And provide the non-graphite olefinic carbon base on the single-layer graphene
Material；The surface more than 10% and less than 80% of wherein described single-layer graphene can be by the non-graphite olefinic carbon base material
Material covering；And the piece of graphene-based material is exposed to the ion energy and 1 × 10 for being characterized in that 5eV to 100keV13It is a from
Son/cm2To 1 × 1021A ion/cm2Fluence ion.In some embodiments, single-layer graphene includes at least two
Surface and the single-layer graphene be more than 10% and the surface less than 80% can be by the non-graphite olefinic carbon base material
Material covering.In some other embodiments, at least a portion of single-layer graphene can be hung.In some embodiments
In, mask or template can be not present between the piece of ion gun and graphene-based material.In some embodiments, ion gun
Can be the ion gun of collimation, such as wide beam or general source.In some embodiments, ion is noble gas ion, selected from Xe+
Ion, Ne+ ions or Ar+ ions, or helium ion.
In some embodiments, ion is selected from Xe+ ions, Ne+ ions and Ar+ ions, and ion energy is 5eV to 50eV
And ion dose is 5 × 1014A ion/cm2To 5 × 1015A ion/cm2.In some embodiments, ion energy is
1keV to 40keV and ion dose are 1 × 1019A ion/cm2To 1 × 1021A ion/cm2.These parameters can be used for
He ions.In some other embodiments, there may be background gas during ionizing radiation.For example, can be 10-3Support
To 10-55 × 10 are included under the gross pressure of support-4Hold in the palm to 5 × 10-5, will in the environment for holding in the palm the oxygen of partial pressure, nitrogen or carbon dioxide
The piece of graphene-based material is exposed to ion.In some embodiments, to include when there are ionizing radiation condition during background gas
The ion energy of 100eV to 1000eV and 1 × 1013A ion/cm2To 1 × 1014A ion/cm2Ion dose.At these
Under the conditions of can use quasi-neutral plasma.
In some embodiments, there is provided the method perforated to the piece of graphene-based material, the described method includes：Institute is provided
The piece of graphene-based material is stated, the graphene-based material includes the single-layer graphene with surface；With offer in the individual layer
Non-graphite olefinic carbon sill on graphene；Wherein described single-layer graphene is more than 10% and the surface quilt less than 80%
The non-graphite olefinic carbon sill covering；And ultraviolet radioactive and oxygen-containing gas are exposed to by described of graphene-based material,
Radiation intensity is 10mW/cm2To 100mW/cm2, continue 60 seconds to 1200 seconds.In some embodiments, single-layer graphene includes
At least two surfaces and the single-layer graphene be more than 10% and the surface less than 80% by the non-graphite olefinic carbon
Sill covers.In some embodiments, at least a portion of single-layer graphene is hung.In some embodiments, from
Mask or template are not present between the piece of component and graphene-based material.
Brief description
Figure 1A and 1B is the part illustrated using UV- oxygen treatments applieds into the piece of the graphene-based material after eleven punch 11
Transmission electron microscope (TEM) image.
Fig. 2A and 2B is to illustrate to use Xe+TEM of the ion into a part for the piece of the graphene-based material after eleven punch 11
Image.
Fig. 3 and Fig. 4 is to illustrate to use Ne+TEM image of the ion into the graphene-based material after eleven punch 11.
Fig. 5 and Fig. 6 is to illustrate to use He+TEM image of the ion into the graphene-based material after eleven punch 11.
It is described in detail
Carbon form as graphene expression, i.e., wherein carbon atom is located at single atom level thin slice or forms the sp of extension2-
In several layergrams (for example, about 20 layers or less) of the fused six-membered rings of hydridization carbon plane lattice.Graphene-based material includes
But it is not limited to, single-layer graphene, multi-layer graphene or the single or multiple lift of interconnection graphene-structured domain and combinations thereof.In some realities
Apply in scheme, graphene-based material further includes the material formed by stacking single or multiple lift graphene film.In some embodiment party
In case, multi-layer graphene includes 2 layers to 20 layers, 2 layers to 10 layers or 2 layers to 5 layers.In some embodiments, multi-layer graphene
Layer be stacked, it is but lower than the order of thin graphite crystal on z directions (perpendicular to basal plane).
In some embodiments, the piece of graphene-based material can be the piece of single or multiple lift graphene or including multiple
The piece in the single or multiple lift graphene-structured domain of interconnection, this can be observed in any known fashion, such as use low-angle electricity
Sub- diffraction, transmission electron microscope etc..In some embodiments, multi-layer graphene domain has 2 to 5 layers or 2 to 10 layers.
As used herein, domain refers to that wherein atom is substantially uniformly ranked into the region of the material of lattice.Domain is in its border
Uniformly, but may be different from adjacent region.For example, monocrystal material has the domain of single atom in order.In some realities
Apply in scheme, at least some graphene-structured domains are nanocrystals, its structure with 1nm to 100nm or 10nm to 100nm
Domain.In some embodiments, the domain size at least some graphene-structured domains is more than 100nm to 1 microns, or is
200nm is to 800nm, or is 300nm to 500nm.In some embodiments, the domain of multi-layer graphene can be with adjacent bonds
Structure domain is overlapping.Can be by the lattice for the crystal boundary area split-phase neighbour that the crystal defect of the edge of each domain is formed.In some realities
Apply in scheme, rotated by the axis around the plane perpendicular to piece, the first lattice can be rotated relative to the second lattice so that two
A lattice is different on crystal lattice orientation.
In some embodiments, the piece of graphene-based material is single or multiple lift graphene or the piece of its combination.One
In other a little embodiments, the piece of graphene-based material is the piece in the single or multiple lift graphene-structured domain for including multiple interconnection.
In some embodiments, the domain of interconnection is covalently bonded together to form piece.When the domain in piece is in crystal lattice orientation
When upper different, piece is polycrystalline.
In some embodiments, the thickness of the piece of graphene-based material for 0.3nm to 10nm, 0.34nm to 10nm,
0.34nm to 5nm or 0.34nm to 3nm.In some embodiments, thickness includes single-layer graphene and non-graphite olefinic carbon.
In some embodiments, the piece of graphene-based material includes the defects of intrinsic or natural.With that will be selectively introducing
The perforation of the piece or graphene film of graphene-based material is on the contrary, the preparation of graphene-based material can cause intrinsic or natural lack
Fall into.The defects of such intrinsic or natural, can include but is not limited to, and lattice exception, hole, tear seam, crackle or wrinkle.Lattice is different
Often it can include but is not limited to, non-6 yuan of carbocyclic rings (such as 5 yuan, 7 yuan or 9 yuan of rings), room, interstitial defect (are included in lattice simultaneously
Enter non-carbon) and crystal boundary.Due to it is intrinsic or natural the defects of or crystal boundary, perforation be different from graphene lattice in opening, but
It is that the test of most telolemma and characterization (such as average pore size etc.) cover all openings, regardless of origin, because they are all
In the presence of.
In some embodiments, graphene is the main material in graphene-based material.For example, graphene-based material can
With comprising at least 20% graphene, at least 30% graphene or at least 40% graphene or at least 50% graphene or at least
60% graphene or at least 70% graphene or at least 80% graphene or at least 90% graphene or at least 95% graphite
Alkene.In some embodiments, graphene-based material include selected from 30% to 95% or 40% to 80%, 50% to 70%,
60% to 95% or 75% to 100% graphene.Include transmission electronic microscope checking using known method, or alternatively such as
Fruit TEM is invalid, is atomic percent by the measurement of the graphene in graphene-based material with the e measurement technology of another like
Than.
In some embodiments, the piece of graphene-based material also includes at least one of the piece positioned at graphene-based material
Non-graphite olefinic carbon sill on surface.In some embodiments, two surface of base (such as the top surface of piece and bottom are passed through
Face, opposite face) and side (such as side of piece) illustrate the piece.In some other embodiments, " bottom " face of piece
It is that and " freedom " face of piece is opposite with " bottom " face in the face of the growth period contact substrate of piece.In some embodiments, it is non-
Graphene carbon sill can be located at one or two substrate surface (such as the substrate side of piece and/or the Free Surface of piece of piece
Face).In some other embodiments, the piece of graphene-based material includes other a small amount of one or more materials on surface
Material, such as, but not limited to, one or more dust particles or similar pollutant.
In some embodiments, the amount of non-graphite olefinic carbon sill is less than the amount of graphene.In some other implementations
In scheme, the amount of non-graphite olefinic carbon material is the three times of the amount of graphene to five times；This is measured according to quality.Other
In some embodiments, non-graphite olefinic carbon material is characterized in that the quality selected from 0% to the 80% graphene-based material
Percentage.In some embodiments, non-graphite olefinic carbon sill is more than the surface coverage of piece zero and is less than 80%, is
5% to 80%, it is 10% to 80%, is 5% to 50% or is 10% to 50%.This surface coverage can use transmitted electron
Microscope measures, it produces projection.In some embodiments, the amount of the graphene in graphene-based material for 60% to
95% or 75% to 100%.Using known method, preferably using transmission electronic microscope checking, or alternatively if TEM is
Invalid, then it is mass percent by the measurement of the graphene in graphene-based material using other similar technologies.
In some embodiments, non-graphite olefinic carbon sill without long-range order and is classified into amorphous
's.In some embodiments, non-graphite olefinic carbon sill is also comprising the element in addition to carbon and/or hydrocarbon.
In some embodiments, the non-carbon element that can be incorporated in non-graphite olefinic carbon includes hydrogen, oxygen, silicon, copper and iron.In some other
In embodiment, non-graphite olefinic carbon sill includes hydrocarbon.In some embodiments, carbon is non-graphene carbon base material
Main material in material.For example, in some embodiments, non-graphite olefinic carbon sill is comprising at least 30% carbon or at least
40% carbon or at least 50% carbon or at least 60% carbon or at least 70% carbon or at least 80% carbon or at least 90% carbon or extremely
Few 95% carbon.In some embodiments, non-graphite olefinic carbon sill include selected from 30% to 95% or 40% to 80% or
50% to 70% carbon.Using known method, preferably using transmission electronic microscope checking, or alternatively if TEM is invalid
, then it is atomic percent by the measurement of the carbon in non-graphite olefinic carbon sill using other similar technologies.
It is suitable for that the puncturing technique of graphene-based material into eleven punch 11 can be included as described herein based on ion
Method for punching and the method based on UV- oxygen.
Method for punching based on ion includes the method that wherein graphene-based material is directed ion source radiation.Other
In some embodiments, ion gun is collimation.In some embodiments, ion gun is wide beam or general source.With focused ion
Beam is compared, and wide field or general ion gun can provide significantly reduced ionic flux.Induce graphene or the perforation of other two-dimensional materials
Ion gun be considered to provide wide ion field, be also generally referred to as the general source of ion.In some embodiments, the general source of ion
Do not include condenser lens.In some embodiments, ion gun less than atmospheric pressure for example 10-3Hold in the palm to 10-5Support or 10-4Support
To 10-6Operated under support.In some embodiments, environment is also comprising background amount (such as about 10-5Support) oxygen (O2)、
Nitrogen (N2) or carbon dioxide (CO2).In some embodiments, ion beam can be perpendicular to the surface (incidence angle of the layer of material
For 0 degree) or incidence angle can be 0 to 45 degree, 0 to 20 degree, 0 to 15 degree or 0 to 10 degree.In some other embodiments,
Do not include being exposed to plasma exposed to ion.
In some embodiments, the method for punching based on UV- oxygen is exposed at the same time including wherein graphene-based material
The method of ultraviolet (UV) light and oxygen-containing gas.Ozone can by by oxygen-containing gas (such as oxygen or air) exposed to UV light and
Produce.Ozone can also be supplied by ozone generator device.In some embodiments, the method for punching based on UV- oxygen
Further include and graphene-based material is exposed to elemental oxygen.The suitable wavelength of UV light includes but not limited to the wavelength less than 300nm
Or the wavelength of 150nm to 300nm.In some embodiments, the intensity at 6mm distances is 10mW/cm2To 100mW/cm2Or
Intensity at 6mm distances is 100mW/cm2To 1000mW/cm2.For example, suitable light (e.g., from about 185nm is launched by mercury discharge lamp
And 254nm).In some embodiments, in room temperature or the progress UV/ oxygen cleanings at a temperature of more than room temperature.Other
In some embodiments, UV/ oxygen cleanings are carried out under atmospheric pressure (such as 1atm) or vacuum.
Perforation is set to size as described herein, to provide material (atom, molecule, albumen for given application
Matter, virus, cell etc.) desired selective penetrated property.Selective penetrated property refers to that porous material or perforation two-dimensional material allow one
Kind or many kinds of substance more easily or pass through more quickly the tendency of (or transmit) than other materials.Selective penetrated property allows to show
The material separation of different through-rates or transmission rate.In two-dimensional material, the size or size (example in selective penetrated property and hole
Such as, diameter) it is related with the relative efficiency size of material.The selection of perforation in two-dimensional material (such as graphene-based material) passes through
Property might also depend on the functionalization of perforation (if any) and predetermined substance.Two or more materials in the mixture
Separation or by being included in mixture by two-dimensional material of perforating during and after, two or more materials in mixture
Ratio (weight or molar ratio) changes.
In some embodiments, the characteristic size of perforation is 0.3nm to 10nm, 1nm to 10nm, 5nm to 10nm, 5nm
To 20nm, 10nm to 50nm, 50nm to 100nm, 50nm to 150nm, 100nm to 200nm or 100nm to 500nm.At some
In embodiment, average pore size is within the specified range.In some embodiments, in sheet or layer 70% to 99%,
80% to 99%, 85% to 99% or 90% to 99% perforation falls within the specified range, but other holes fall in specified model
Outside enclosing.
The nano material for producing hole intentionally is properly termed as perforation graphene, the graphene-based material of perforation or perforation two dimension material
Material etc..Graphene-based material of perforating includes the material that wherein non-carbon is merged in the edge of hole.Pore character and other materials
Material feature can characterize in a variety of ways, including with the relevant side such as size, area, domain, periodicity, the coefficient of variation
Formula.For example, pore-size can be assessed by quantitative image analysis using image, described image is preferably shown by transmitted electron
Micro mirror obtains, and if TEM is invalid, is obtained by scanning electron microscope etc., such as illustrated in fig. 1 and 2.Material
Presence and the boundary marking that the is not present profile of hole.Unless otherwise stated, the size of hole can pass through expection
Material is determined with being imaged the form fit of hole profile, and wherein size measures are characterized with minimum dimension.For example, in some feelings
Under condition, shape can be circular or ellipse.Circle shows the constant and minimum size equal with its diameter.Elliptical width
Degree is its minimum size.Unless otherwise stated, the diameter and width measure of form fit in these cases provide
Size measures.
Each pore-size of test sample can be measured with the distribution of definite test sample inner pore size.It can also survey
Measure other specification, such as area, domain, periodicity, coefficient of variation etc..Multiple test samples can be taken to larger film with true
The uniformity for determining result suitably characterizes whole film.In such a case, it is possible to come by using the performance of test substances test film
Confirm result.It is restricted for example, if measurement shows that the material of some sizes should pass through in transmission on film, performance test
Verification is provided with test substances.Alternatively, performance test may be used as indicant, and hole measurement will determine consistent hole ruler
Very little, area, domain, periodicity, coefficient of variation etc..
The Size Distribution of hole can be narrow, for example, being limited to less than 0.1 to 0.5 coefficient of variation.In some embodiment party
In case, the characteristic size of hole is selected to be used to apply.
In some embodiments of circular fit are related to, by equation A=π d2/ 4 calculate the equivalent diameter of each hole.
In addition, area is the function of form fit.When function plotting of the pore area as equivalent pore diameter, hole can be obtained
Size Distribution.The coefficient of variation of pore-size can be calculated as to the pore-size such as measured in whole test sample herein
Standard deviation and pore-size average value ratio.The average area of perforation is the hole such as measured in whole test sample
The average measurement area of gap.
In some embodiments, the area ratio of perforation can be used for being characterized as wearing by piece compared to the area ratio of piece
The density in hole.The area of test sample can be as the area of plane crossed over by test sample.Due to making other non-planar features
Corrugate, the surface area of piece in addition can exclude.Characterize ratio conduct that can be based on perforation field and test sample area
Density of such perforation, excludes the feature of such as surface patches.Characterization can the ratio based on the suspension area of perforation field and piece.With it
He tests equally, can take multiple test samples to confirm the uniformity entirely tested, and can be obtained by performance test
Verification.Density of such perforation can be for example, per nm2For 2 (2/nm2) to every μm2For 1 (1/ μm2)。
In some embodiments, perforation field accounts for 0.1% or bigger of piece area, 1% or bigger or 5% or bigger,
10% less than piece area, 15% less than piece area, be piece area 0.1% to 15%, the 1% to 15% of piece area, piece
The 5% to 15% of area or the 1% to 10% of piece area.In some other embodiments, perforation is located at the graphene
The piece of sill is more than on 10% or the area more than 15%.The piece of macro-scale is macroscopical, and can be seen with naked eyes
Observe.In some embodiments, at least one lateral dimension of piece be more than 3cm, more than 1cm, more than 1mm or more than 5mm.
In addition in some embodiments, piece is bigger than graphene platelet, and the graphene platelet can be by for manufacturing graphene
Graphite is peeled off in the known method of thin slice and is obtained.For example, the lateral dimension of piece is greater than about 1 micron.In other embodiments
In, the lateral dimension of piece is less than 10cm.In some other embodiments, the lateral dimension of piece is (for example, the thickness perpendicular to piece
Degree) it is that 10nm to 10cm or more than 1mm and is less than 10cm.
The chemical vapor deposition growth of graphene-based material is usually directed to using carbonaceous precursor materials, such as methane and growth
Substrate.In some embodiments, growth substrates are metal growth substrates.In some embodiments, metal growth substrates are
Substantially continuous metal layer, rather than grid or grid.Compatible metal is grown with the growth of graphene and graphene-based material
Substrate includes transition metal and its alloy.In some embodiments, metal growth substrates are based on copper or based on nickel.
In some embodiments, metal growth substrates are copper or nickel.In some embodiments, graphene-based material is given birth to by dissolving
Long substrate is removed from growth substrates.
In some embodiments, by chemical vapor deposition (CVD), then advance to a few other adjusting or place
Reason step forms the piece of graphene-based material.In some embodiments, regulating step be selected from heat treatment, UV- oxygen treatments applieds, from
Beamlet processing and combinations thereof.In some embodiments, heat treatment can be included in 10-7It is heated under support to the pressure of atmospheric pressure
200 DEG C to 800 DEG C of temperature, continue 2 hours to 8 it is small when.In some embodiments, UV- oxygen treatments applieds can be related to exposure
In the light of 150nm to 300nm, and the intensity at 6mm distances is 10mW/cm2To 100mW/cm2, continue 60 seconds to 1200
Second.In some embodiments, UV- oxygen treatments applieds can carry out at a temperature of room temperature or more than room temperature.In some other
In embodiment, UV- oxygen treatments applieds can carry out under atmospheric pressure (such as 1atm) or vacuum.In some embodiments, from
Beamlet processing, which can be related to, to be exposed to ion energy for 50eV to 1000eV (being used to pre-process) by graphene-based material and notes
Measure as 3 × 1010A ion/cm2To 8 × 1011A ion/cm2Or 3 × 1010A ion/cm2To 8 × 1013A ion/cm2(use
In pretreatment) ion.In some other embodiments, ion gun can be collimated, such as wide beam or general source.One
In a little embodiments, ion can be noble gas ion, such as Xe+.In some embodiments, by graphene-based material
One or more regulating steps are carried out when being attached to substrate (such as growth substrates).
In some embodiments, adjusting processing influences the mobility and/or volatility of agraphitic carbon sill.At some
In embodiment, the surface mobility of non-graphite olefinic carbon sill is so as to be radiated when with all penetrating parameters as described herein
When, non-graphite olefinic carbon sill can have so that perforation procedure ultimately results in the surface mobility of perforation.It is not intended to be taken office
The constraint of what specific idea, it is believed that hole formation is filled with removing the carbon of beam induction from graphene film and being vulcanized by non-graphite olefinic carbon
Carbon in perforated is related.Supplement process can depend on the energy and non-graphite olefinic carbon base material for entering system during perforation
The surface mobility of the gained of material.In order to form hole, the removal rate of graphene can be higher than non-graphite olefinic carbon holes filling
Speed.These competition speed depend on non-graphite olefinic carbon flux (such as mobility [viscosity and temperature] and quantity) and graphene is gone
Removal rates (such as granular mass, energy, flux).
In some embodiments, the volatility of non-graphite olefinic carbon sill can be than by vacuum or having indifferent gas
Under the atmospheric pressure of body by the piece of graphene-based material be heated to 500 DEG C continue 4 it is small when and the volatility that obtains is small.
In various embodiments, CVD graphenes or graphene-based material can be discharged from its growth substrate (for example, Cu)
And it is transferred to support grid, grid or other supporting structures.In some embodiments, can by support structure configuration into
So that at least some partial suspensions of the piece of graphene-based material are in supporting structure.For example, the piece of graphene-based material is at least
Some parts can not be contacted with supporting structure.
In some embodiments, the piece of the graphene-based material after chemical vapor deposition, which includes, has at least two
The single-layer graphene on surface, and non-graphite olefinic carbon sill can be provided on the surface of single-layer graphene.At some
In embodiment, non-graphite olefinic carbon sill can be located at one of two surfaces above or on two surfaces.Other one
In a little embodiments, graphene carbon in addition can also be present on the surface of single-layer graphene.
By following non-limiting example it will be further appreciated that preferred embodiment.
Embodiment：Perforate graphene-based material
Figure 1A and Figure 1B is the part illustrated using UV- oxygen treatments applieds into the piece of the graphene-based material after eleven punch 11
TEM image.Figure 1B shows the amplifier section of Figure 1A.Label 10 represents the region of graphene, and brighter peripheral region mainly wraps
Non-graphite olefinic carbon is included, and dark area is hole.By preparing graphene through chemical vapor deposition sill, then grown in copper
When on substrate with Xe ions under 80 DEG C and 500V with 1.25 × 1013A ion/cm2Fluence be subjected to ion beam.Then
TEM grids are transferred the material to, with described ultraviolet (UV) parameter under the atmospheric pressure with atmospheric gas when then hanging
Receive the processing of 400 seconds.Intensity at 6mm is 28mW/cm2。
Fig. 2A and Fig. 2 B are the TEM illustrated using Xe ions into a part for the piece of the graphene-based material after eleven punch 11
Image.Fig. 2 B show the amplifier section of Fig. 2A.By preparing graphene through chemical vapor deposition sill, pre-processed, then
It is transferred to TEM grids and is radiated under 20V and 2000nAs with Xe ions.2000nAs=1.25 × 1015A ion/cm2。
The area % of hole is 5.8%.
Fig. 3 and Fig. 4 is the TEM image illustrated using Ne ions into the graphene-based material after eleven punch 11.Fig. 4 be in compared with
Under high amplification factor.By preparing graphene through chemical vapor deposition sill, pre-processed, be then transferred to TEM grids
And with 4 × 10 under 23kV17The fluence of a ion/cm is radiated with Ne ions.
Fig. 5 and Fig. 6 is the TEM image illustrated using He ions into the graphene-based material after eleven punch 11.Fig. 6 be in compared with
Under high amplification factor.By preparing graphene through chemical vapor deposition sill, pre-processed, be then transferred to TEM grids
And with 1 × 10 under 25kV20A ion/cm2Fluence radiated with He ions.
Perforation is typically shown as the darker area in these images.
Although describing present disclosure by reference to disclosed embodiment, those of ordinary skill in the art will
It is readily appreciated that, these disclosures being merely an illustrative.It should be understood that in the feelings without departing substantially from purport in the present disclosure
Various modifications can be carried out under condition.Can change any number of change that present disclosure do not describe so far with being incorporated to,
Change, replacement or equivalent arrangements, but it is suitable with spirit and scope in the present disclosure.In addition, although it have been described that originally
The various embodiments of disclosure, but it is to be understood that aspect in the present disclosure can only include some described embodiment party
Case.Therefore, present disclosure is not construed as being subject to previously described limitation.
Unless otherwise stated, the various preparations or combination of described or exemplary component can be used for putting into practice embodiment party
Case.The specific name of compound is intended to be exemplary, because it is known that those of ordinary skill in the art can differently name phase
Same compound.When compound being described as herein so that for example in formula or in chemical name, the not specified compound
When specific isomers or enantiomer, which is intended to include the every kind of different of compound individually describing or describing in any combination
Structure body and enantiomer.It will be understood by those skilled in the art that the method, apparatus member in addition to those of specific example
Part, starting material and synthetic method can be used for practice embodiments, and not against excessive experiment.Any such method, dress
All known functional equivalents for putting element, starting material and synthetic method are intended to and are comprised in embodiment.Whenever
When providing scope in the description, for example, temperature range, time range or compositing range, all intermediate ranges and subrange
And all single values in given range are intended to and are comprised in present disclosure.When Markush used herein
When group or other packets, all separate members of the group and all possible combination of the group and sub-portfolio are intended to individually
Including in this disclosure.
As used herein, "comprising" and " comprising ", " containing " or " being characterized in that " are synonymous, and be inclusive or
Open, and it is not excluded for the other element not described or method and step.As used herein, " Consists of " excludes wanting
Ask unspecified any element, step or component in the element of protection.As used herein, "consisting essentially of ..." is not excluded for reality
The fundamental characteristics of claim and the material of novel characteristics or step are not influenced in matter.Herein any of term "comprising" chats
State, particularly in the description of the component of composition or in the description of the element of device, it is thus understood that cover substantially by institute
Component or the element composition of narration and the composition and method that are made of cited component or element.Can not have herein
Property description illustrated herein is compatibly put into practice in any element, limitation disclosed in body embodiment in the case of being not present.
The terms and expressions used are used as descriptive term rather than restricted term, and it is not intended that
With the such terms and expressions for any equivalent for excluding shown and described feature or its part, and will be appreciated that can
To carry out various modifications in the range of embodiment claimed.Although it will thus be appreciated that by preferred feature and
Optional feature has specifically disclosed some embodiments, but those skilled in the art can take concept disclosed herein
Modification and variation, and such modification and variation are considered as the scope in the embodiment being indicated in the appended claims
It is interior.
In general, terms used herein and phrase have its art-recognized implication, this can be by reference to this area
Received text, journal references and background known to technical staff are found.Any previous definition is provided with preferred real
Their particular use is illustrated in the case of applying scheme.
In entire chapter the application all referring to document, such as including the patent announced or authorized or the patent of equivalent
File；Patent Application Publication；With Non Patent Literature Documents or the material in other sources；Herein this is integrally incorporated by quoting
Text, it is consistent with the disclosure in the application at least in part to every bibliography as being individually incorporated to by quoting
Degree (for example, the inconsistent bibliography in part is incorporated by reference into, but except the inconsistent part in the part of the bibliography with
Outside).
The all patents and publications referred in specification shows the skill of preferred embodiment those skilled in the art
Art is horizontal.References cited herein is incorporated herein by reference in their entirety to show the state of technology, untill its applying date
Certain situation under, and if desired, it is meant that can use this information to exclude (for example, abandoning) herein existing
Particular in technology.For example, when claimed compound, it should be appreciated that well known in the prior artization
Some compounds (particularly in cited patent file) disclosed in compound, including bibliography disclosed herein, no
It is intended to comprising in the claims.
Claims (45)
1. the perforated sheet of graphene-based material, have area and comprising：
The single-layer graphene of perforation；
Multiple perforation in the single-layer graphene, it is located on the area more than 10% of the single-layer graphene, institute
The average pore size for stating perforation is selected from 0.3nm to 1 μm；
Wherein described perforation is characterized in that density of such perforation is selected from 2/nm2To 1/ μm2；Also,
Wherein described perforation field corresponds to the area of 0.1% or bigger of the piece of the graphene-based material.
2. the perforated sheet of graphene-based material as claimed in claim 1, wherein the perforation be characterized by having with 0.1 to
The distribution of pores for the dispersion degree that 2 coefficient of variation is characterized.
3. the perforated sheet of graphene-based material as claimed in claim 2, wherein the single-layer graphene is characterized in that being more than
Or the average-size domain of the long-range order equal to 1 μm.
4. the perforated sheet of graphene-based material as claimed in claim 1, wherein the single-layer graphene has with 1 micron of quantity
The unordered degree that the long-range lattice period of level is characterized.
5. the perforated sheet of graphene-based material as claimed in claim 1, the graphene-based material of its middle punch do not show to grow
Journey order.
6. the perforated sheet of graphene-based material as claimed in claim 1, wherein at least one transverse direction of the single-layer graphene
Size is 10nm to 10cm.
7. the perforated sheet of graphene-based material as claimed in claim 6, wherein the single-layer graphene includes at least two tables
Face and the single-layer graphene be more than 10% and the surface less than 80% is covered by non-graphite olefinic carbon sill.
8. the perforated sheet of graphene-based material as claimed in claim 7, wherein the non-graphite olefinic carbon sill and the list
At least one physical contact in the surface of layer graphene.
9. the perforated sheet of graphene-based material, comprising：
The single-layer graphene of perforation with multiple perforation, the perforation are characterized in that the perforation positioned at described graphene-based
The piece of material more than 10% the area on and the perforation average pore size be selected from 0.3nm to 1 μm.
10. the perforated sheet of graphene-based material, the graphene-based material includes：
Single-layer graphene；
Multiple perforation in the single-layer graphene, the perforation are characterized in that the perforation is located at the graphene-based material
Piece more than 10% the area on and the perforation average pore size be selected from 0.3nm to 1 μm.
11. the perforated sheet of the graphene-based material as described in claim 9 or 10, wherein the perforation be characterized by having with
The distribution of pores for the dispersion degree that 0.1 to 2 coefficient of variation is characterized.
12. the perforated sheet of the graphene-based material as described in claim 9 or 10, wherein the coefficient of variation of the pore-size is
0.5 to 2.
13. the perforated sheet of the graphene-based material as described in claim 9 or 10, wherein the coefficient of variation of the pore-size is
0.1 to 0.5.
14. the perforated sheet of the graphene-based material as any one of claim 9 to 13, wherein the feature of the perforation exists
In selected from 2/nm2To 1/ μm2Density of such perforation.
15. the perforated sheet of the graphene-based material as any one of claim 9 to 14, wherein perforation field correspond to institute
State the area of 0.1% or bigger of the piece of graphene-based material.
16. the piece of the graphene-based material as any one of claim 9 to 15, wherein the perforation is characterized in that selecting
From 0.2nm2To 0.25 μm2The perforation average area.
17. the perforated sheet of graphene-based material as claimed in claim 9, wherein the single-layer graphene is characterized in that being more than
Or the average-size domain of the long-range order equal to 1 μm.
18. the perforated sheet of graphene-based material as claimed in claim 9, wherein the single-layer graphene has with 1 micron number
The unordered degree that the long-range lattice period of magnitude is characterized.
19. the perforated sheet of graphene-based material as claimed in claim 9, wherein the single-layer graphene, which has, is characterized in that small
In the unordered degree of the lattice defect of 1% content.
20. the perforated sheet of graphene-based material as claimed in claim 9, wherein the lattice of the single-layer graphene in 1nm extremely
Destroyed in the scale of 10nm.
21. the perforated sheet of graphene-based material as claimed in claim 10, wherein the graphene-based material of perforation does not show
Go out long-range order.
22. the perforated sheet of the graphene-based material as any one of claim 9 to 21, wherein the thickness of described is
0.3nm to 10nm.
23. the perforated sheet of the graphene-based material as any one of claim 9 to 22, wherein described at least one
Lateral dimension is 10nm to 10cm.
24. the perforated sheet of the graphene-based material as described in claim 9 or 10, also comprising offer on the single-layer graphene
Non-graphite olefinic carbon sill.
25. the perforated sheet of graphene-based material as claimed in claim 24, wherein the single-layer graphene includes at least two
Surface and the single-layer graphene be more than 10% and the surface less than 80% is covered by the non-graphite olefinic carbon sill
Lid.
26. the perforated sheet of graphene-based material as claimed in claim 24, wherein the non-graphite olefinic carbon sill with it is described
At least one physical contact in the surface of single-layer graphene.
27. the perforated sheet of graphene-based material as claimed in claim 24, wherein the non-graphite olefinic carbon sill does not show
Go out long-range order.
28. the perforated sheet of graphene-based material as claimed in claim 24, wherein the non-graphite olefinic carbon sill has bag
The element of carbon containing, hydrogen and oxygen forms.
29. the perforated sheet of graphene-based material as claimed in claim 24, wherein the non-graphite olefinic carbon sill has bag
Containing amorphous carbon, one or more hydrocarbons, point containing carbon oxygen compound, nitrogenous carbon compound or any combination of these
Son composition.
30. the perforated sheet of graphene-based material as claimed in claim 24, wherein the non-graphite olefinic carbon sill includes
10% to 100% carbon.
31. the perforated sheet of graphene-based material as claimed in claim 24, wherein the non-graphite olefinic carbon sill also includes
Non-carbon element.
32. the perforated sheet of graphene-based material as claimed in claim 31, wherein the non-carbon element is selected from hydrogen, oxygen, silicon, copper
And iron.
33. the perforated sheet of graphene-based material as claimed in claim 31, wherein the feature of the non-graphite olefinic carbon sill
It is substantially limited mobility.
34. the perforated sheet of graphene-based material as claimed in claim 31, wherein the non-graphite olefinic carbon sill is basic
Non-volatile.
35. the method for making the piece of graphene-based material perforate, the described method includes：
The piece of the graphene-based material is positioned, the graphene-based material includes the mono-layer graphite with least two surfaces
Alkene；With non-graphite olefinic carbon sill of the offer on the single-layer graphene；Wherein described single-layer graphene be more than 10% and
The surface less than 80% is covered by the non-graphite olefinic carbon sill；And
The piece of the graphene-based material is exposed to ion, the ion is characterized in that the ion energy of 10eV to 100keV
With 1 × 1013A ion/cm2To 1 × 1021A ion/cm2Fluence.
36. method as claimed in claim 35, wherein providing the ion by the general source of ion.
37. method as claimed in claim 35, wherein the ion is noble gas ion.
38. method as claimed in claim 35, wherein the ion is selected from Xe+Ion, Ne+Ion or Ar+Ion.
39. method as claimed in claim 38, wherein ion energy are 5keV to 50keV and ion dose is 5 × 1014It is a
Ion/cm2To 5 × 1015A ion/cm2。
40. method as claimed in claim 38, wherein 10-3Hold in the palm to 10-55 × 10 are being included under the stagnation pressure of support-4Support to 5 ×
10-5In the environment for holding in the palm the oxygen of partial pressure, nitrogen or carbon dioxide, the piece of the graphene-based material is exposed to the ion.
41. method as claimed in claim 38, wherein the ion energy is the ion energy of 100eV to 1000eV, and
The ion dose is 1 × 1013A ion/cm2To 1 × 1014A ion/cm2。
42. method as claimed in claim 35, wherein the ion is helium ion.
43. method as claimed in claim 42, wherein the ion energy is the ion energy of 1keV to 40keV and described
Ion dose is 1 × 1019A ion/cm2To 1 × 1021A ion/cm2。
44. the method for making the piece of graphene-based material perforate, the described method includes；
The piece of the graphene-based material is positioned, the graphene-based material includes the mono-layer graphite with least two surfaces
Alkene；With non-graphite olefinic carbon sill of the offer on the single-layer graphene；Wherein described single-layer graphene be more than 10% and
The surface less than 80% is covered by the non-graphite olefinic carbon sill；And
Distance in 6mm, with 10mW/cm2To 100mW/cm2Radiation intensity by the piece of the graphene-based material exposed to purple
External radiation and oxygen-containing gas continue 60 seconds to 1200 seconds.
45. method as claimed in claim 44, wherein the oxygen-containing gas is the air under atmospheric pressure.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201562201527P | 2015-08-05 | 2015-08-05 | |
| US201562201539P | 2015-08-05 | 2015-08-05 | |
| US62/201,527 | 2015-08-05 | ||
| US62/201,539 | 2015-08-05 | ||
| PCT/US2016/027612 WO2017023378A1 (en) | 2015-08-05 | 2016-04-14 | Perforated sheets of graphene-based material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107921402A true CN107921402A (en) | 2018-04-17 |
Family
ID=61683171
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680045785.1A Pending CN107921402A (en) | 2015-08-05 | 2016-04-14 | The perforated sheet of graphene-based material |
| CN201680045782.8A Pending CN107847835A (en) | 2015-08-05 | 2016-04-14 | Pierceable of graphene-based material |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201680045782.8A Pending CN107847835A (en) | 2015-08-05 | 2016-04-14 | Pierceable of graphene-based material |
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| Country | Link |
|---|---|
| EP (2) | EP3331644A4 (en) |
| CN (2) | CN107921402A (en) |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5902723B2 (en) * | 2011-03-15 | 2016-04-13 | プレジデント アンド フェローズ オブ ハーバード カレッジ | Controlled fabrication of nanopores in nanometer semiconductor materials |
| US9056282B2 (en) * | 2012-01-27 | 2015-06-16 | Empire Technology Development Llc | Accelerating transport through graphene membranes |
| EP2825508A4 (en) * | 2012-03-15 | 2015-10-21 | Massachusetts Inst Technology | Graphene based filter |
| SG11201405346RA (en) * | 2012-03-21 | 2014-10-30 | Lockheed Corp | Methods for perforating graphene using an activated gas stream and perforated graphene produced therefrom |
| EP2969153A1 (en) * | 2013-03-13 | 2016-01-20 | Lockheed Martin Corporation | Nanoporous membranes and methods for making the same |
| US9610544B2 (en) * | 2013-12-04 | 2017-04-04 | The United States Of America As Represented By Secretary Of The Navy | Method for creating a nano-perforated crystalline layer |
| CN105940479A (en) * | 2014-01-31 | 2016-09-14 | 洛克希德马丁公司 | Methods for perforating two-dimensional materials using a broad ion field |
-
2016
- 2016-04-14 EP EP16833429.0A patent/EP3331644A4/en not_active Withdrawn
- 2016-04-14 CN CN201680045785.1A patent/CN107921402A/en active Pending
- 2016-04-14 CN CN201680045782.8A patent/CN107847835A/en active Pending
- 2016-04-14 EP EP16833431.6A patent/EP3331816A4/en not_active Withdrawn
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| Publication number | Publication date |
|---|---|
| EP3331644A1 (en) | 2018-06-13 |
| EP3331816A1 (en) | 2018-06-13 |
| CN107847835A (en) | 2018-03-27 |
| EP3331816A4 (en) | 2019-03-27 |
| EP3331644A4 (en) | 2019-09-11 |
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