EP3331824A1 - Nanoparticle modification and perforation of graphene - Google Patents
Nanoparticle modification and perforation of grapheneInfo
- Publication number
- EP3331824A1 EP3331824A1 EP16833430.8A EP16833430A EP3331824A1 EP 3331824 A1 EP3331824 A1 EP 3331824A1 EP 16833430 A EP16833430 A EP 16833430A EP 3331824 A1 EP3331824 A1 EP 3331824A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- graphene
- nanoparticles
- based material
- sheet
- layers
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- 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
- C01B32/182—Graphene
- C01B32/194—After-treatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/009—After-treatment of organic or inorganic membranes with wave-energy, particle-radiation or plasma
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
Definitions
- the present disclosure generally relates to graphene based materials and other two-dimensional materials, and, more specifically, to methods for producing pores in layers of graphene, other two-dimensional materials and combinations thereof.
- Graphene has garnered widespread interest for use in a number of applications due to its favorable mechanical and electronic properties.
- the electrical conductivity of graphene can be influenced by the amount and type of chemical functionalization on the graphene and the quantity of defects in the graphene basal plane.
- pristine graphene typically displays the highest electrical conductivity values, it can sometimes be desirable to tune the electrical conductivity and modify the band structure. Tailoring of the band structure can be accomplished, for example, by introducing a plurality of defects (i.e., holes or perforations) within the graphene basal plane or increasing the number of such defects.
- the band structure can be influenced by both the size, type, and number of holes present.
- a two dimensional material has a thickness of 0.3 to 1.2 nm. In another embodiment, a two dimensional material has a thickness of 0.3 to 3 nm.
- molybdenum sulfide is a representative chalcogenide having a two-dimensional molecular structure, and other various chalcogenides can constitute the two-dimensional material in the present disclosure.
- Two-dimensional materials include metal chalogenides (e.g., transition metal dichalogenides), transition metal oxides, hexagonal boron nitride, graphene, silicene and germanene (see: Xu et al. (2013) "Graphene-like Two-Dimensional Materials) Chemical Reviews 1 13 :3766-3798).
- the present disclosure describes methods for introducing or modifying pores in the basal plane of a plurality of graphene sheets stacked upon one another.
- the methods involve exposing about 2-10 layers of stacked graphene sheets (i.e., multi-layer graphene) to a particle beam comprising nanoparticles (NPs) or clusters having an energy of about 2 keV or greater (per nanoparticle or clusters) to perforate the stacked graphene sheets.
- NPs nanoparticles
- the methods described herein are also applicable to other multi-layered 2D materials and to combinations of layered 2D materials.
- the present disclosure further describes methods including the step of exposing a sheet of graphene-based material to a particle or cluster beam, the graphene- based material comprising multi -layer graphene having from 2 to 10 layers of graphene and the particle beam comprising nanoparticles or clusters as described herein.
- the multi-layer graphene has from 2 to 5 layers of graphene.
- the nanoparticle or cluster energy may be greater than or equal to about 2 keV but less than about 500 keV, greater than 2 keV and less than 100 keV, greater than 2 keV and less than 50 keV or greater than or equal to 2 keV and less than or equal to 30 keV.
- the nanoparticle may comprise a plurality of atoms and the energy is from 0.05 eV to 50 eV per atom, 0.1 eV to 50 eV per atom, or leV to IkeV per atom.
- the fluence is lxlO 8 - lxlO 12 Ps/cm 2 .
- the nanoparticle perforation efficiency is from 1% to 100%.
- the methods disclosed herein further include steps for nanoparticle generation and subsequent acceleration.
- the potential is from 1 to 100 kV.
- additional ionization is done such as electron impact and electrospray to provide additional energy to the Ps for perforations.
- Ps columbic limitation may limit the amount of charge (too much charge may cause the particle to fragment).
- the charge is up to 4e.
- the nanoparticles are from 1 nm to 100 nm, 1 nm to 50 nm,
- the NPs are characterized by a uniform size distribution, in other instances by a Gaussian size distribution, in some cases by a normal distribution and still further in other instances in a bimodal distribution.
- both modes are used for perforation and in other embodiments one mode is utilized for perforation and the other for adding additional energy to the graphene.
- the distribution of NP sizes is not a standard distribution.
- the graphene-based material is pretreated before exposure to the beam of nanoparticles.
- a multi-layer graphene-based material is pretreated as a unit.
- layers of graphene-based material are pretreated individually before being stacked.
- the whole layer is treated while in other embodiments the selected regions of the sheet are treated.
- selected regions of the sheet are treated so that the sheet as whole perforates uniformly.
- the pretreatment process introduces point defects into one or more sheets of graphene.
- the pretreatment process introduces pores having an average size less than 1 nm.
- the multi-layered stack of graphene sheets is pretreated as a unit.
- one or more individual graphene sheets are pretreated before assembly into a stack.
- the pretreatment step is selected from thermal treatment, UV- oxygen treatment, ion beam treatment, and combinations thereof.
- the graphene-based materials are irradiated with a broad ion beam having an ion energy from 50 eV to lOkeV and a fluence from 3 x 10 10 ions/cm 2 to 8 x 10 11 ions/cm 2 or 3 x 10 10 ions/cm 2 to 8 x 10 13 ions/cm 2 .
- the irradiation time is from 0.1 milliseconds to less than 10 seconds, from 1 millisecond to less than 10 seconds, from 1 second to 100 seconds, or from 10 second to 1000 seconds. In general, if relatively small areas are irraditated then the times are lower than when relatively larger areas are irradiated.
- the pretreatment process irradiates the graphene to introduce moieties into the graphene lattice to weaken it and make it more easily perforated with nanoparticles. Such a pretreatment process can enable "chemically assisted" perforation. An example of such a moiety is an oxygen containing compound.
- suitable moieties are introduced with nanoparticle pretreatment.
- the graphene-based material is non-perforated prior to exposure to the nanoparticle beam.
- the graphene-based material is perforated prior to exposure to the nanoparticle beam ("pre-perforated").
- a first layer of graphene is perforated, and then subsequently additional layers of graphene are perforated after the additional layers are applied to the first layer.
- perforation methods are known to the art, including ion-based methods and oxidation based methods.
- the pre-peforated graphene-based material comprises a first set of pores having a first pore size and exposure to the nanoparticle beam then modifies the pre-perforated sheet of graphene-based material.
- the modification includes creating a second set of pores having a second pore size extending through the multiple graphene sheets, modifying the first pore size or combinations thereof.
- the pore size of the perforated graphene-based materials has a bimodal distribution. Exemplary combinations of pore sizes include, but are not limited to a combination of pores with a size less than 3 nm and pores with a size greater than 15 nm and less than or equal to 100 nm. The combinations could be formed through a combination of pre-perforation and P perforation, but also could be formed from combinations of P perforation.
- the ratio of the area of pores with a size less than 3 nm to the area of the sheet is from 1 to 10% while the ratio of the area of pores with a size greater than 15 nm and less than or equal to 100 nm to the area of the sheet is from 1 to 10%.
- exposure of the graphene-based material to the nanoparticle beam perforates the graphene layers to different degrees.
- at least one layer of the graphene is not perforated.
- at least one layer of the graphene is perforated.
- after exposure of the graphene-based material to the nanoparticle beam at least one layer is highly perforated and at least one layer is not perforated.
- a first layer of graphene is perforated with
- a second layer of graphene is transferred to the first layer.
- the second layer is perforated with nanoparticles to obtain pores of a second size, with the perforation conditions being selected so that the nanoparticles used in the second perforation step do not penetrate the first layer.
- the first pore size and the second pore size are different.
- the first pore size is larger than the second pore size.
- the first layer of graphene is perforated using a plurality of a first type of nanoparticle and the second layer of graphene is perforated using a plurality of a second type of nanoparticle.
- the first type of nanoparticle may differ in size and/or composition than the second type of nanoparticle.
- the nanoparticle bombardment takes place while the graphene-based material is disposed on a porous substrate.
- the supporting structure is configured so that at least some portions of the sheet of graphene- based material are suspended from the supporting structure.
- Suitable substrates include, but are not limited to polymeric, silicon nitride (SiN), ceramics, carbon or metal substrates.
- each suspended area is greater than 10 nm and less than 10 micrometers.
- at least one dimension of the opening in the supporting structure is less than 1 ⁇ or less than or equal to 100 nm.
- the substrate may be patterned to provide at least one through-hole of a specified ratio of perimeter to area in order to control the stiffness of the composite graphene-based material and substrate.
- the through hole takes the form of one or more circular holes or one or more slots, which may alternatively be termed slits.
- the slits may be parallel or crossed.
- the slits may have an aspect ratio from 2: 1 to 100: 1.
- the graphene-based material may be removed from the substrate after perforation and transferred to a different substrate.
- the graphene-based material is "in front" of the substrate with respect to the source of nanoparticles. In another embodiment, the graphene-based material is "behind” the substrate with respect to the source of nanoparticles, such that the nanoparticles pass through holes in the substrate before contacting the graphene-based material. In an embodiment where perforation occurs through the substrate, the ratio of thickness of the substrate to the pore diameter is less than 2 (e.g. 500nm diameter pores in ⁇ ⁇ thick substrate). One benefit to this configuration is to only impact and possibly damage or perforate the graphene where it is suspended (through the substrate pores).
- the face of the substrate facing the nanoparticle beam is coated with a sacrificial layer so that all NPs either hit it or perforate the graphene.
- the sacrificial layer can then be removed along with the nanoparticles, leaving perforated graphene on a substrate. This is beneficial when having NPs embedded in the substrate is detrimental.
- an assembly is formed of a first layer of graphene- based material on a first side of a porous substrate and a second layer of graphene-based material on the second side of the porous substrate.
- the substrate is selected to be sufficiently thin that when the assembly is exposed to a particle beam comprising nanoparticles or clusters, the nanoparticles or clusters can penetrate through the assembly and perforate both layers of graphene-based material.
- the first layer of graphene-based material is the same as the second layer of graphene based material, or the first layer is of a first type of graphene-based material and the second layer is of a second type of graphene-based material.
- a first layer of graphene-based material is placed on a first side of an insulating substrate and a second layer of graphene-based material is placed on a second side of the insulating substrate.
- the first and second layer can then be biased separately.
- the first layer of graphene-based material is the same as the second layer of graphene based material, or the first layer is of a first type of graphene- based material and the second layer is of a second type of graphene-based material.
- a first layer of a graphene-based material or other two dimensional material is placed on a first side of an insulating substrate and a second layer of graphene-based material or other two-dimensional material is placed on a second side of the insulating substrate.
- the perforated sheet of graphene-based material may be modified with a post-perforation treatment process.
- exemplary post-perforation treatment processes include, but are not limited to, further dilation of the pores, reshaping of the pores, stabilization of the pores and increasing the fracture toughness of the sheet.
- further dilation of the pores may be achieved by irradiating the perforated graphene sheet with a broad ion beam.
- the ions are selected from the group consisting of Xe, Ne, He, Ga and Ar and the ion energy ranges from 5eV or 40keV and the ion flux or beam density ranges from 1x10 12 ions/cm 2 /s to 1x1013 ions/cm 2 /s, and fluences from 6.24xl0 lj ions/cm 2 to 6.24xl0 14 ions/cm 2 .
- the ions are selected from the group consisting of Xe, Ne, and Ar, the ion energy ranges from 5 eV to 40 keV, with an exemplary embodiment of lOOeV to lOOOeV and the ion dose ranges from lxlO ions/cm 2 to 5xl0 15 ions/cm 2 .
- the ion energy ranges from 1 keV to 40 keV and the ion dose ranges from 1x10 19 ions/cm 2 to 1x1021 ions/cm 2.
- the ion energy is 300 V and the ion dose is lxlO 14 ions/cm 2 .
- a rastered focused ion beam can be used instead of a broad ion beam.
- dilation of the pores is accompanied by an increase in the overall percentage of porosity.
- reshaping of the pores may be achieved by irradiating the perforated graphene sheet with a broad ion beam.
- the ions are selected from the group consisting of Xe ions, Ne ions, and Ar ions and the ion energy ranges from 10 eV to 10 keV and the ion flux or beam density ranges from from lxlO 12 ions/cm 2 /s to lxlO 13 ions/cm 2 /s, and fluences from 6.24xl0 13 ions/cm 2 to 6.24xl0 14 ions/cm 2 ..
- stabilization of the pores may be achieved by irradiating the perforated graphene sheet with a broad ion beam, wherein the ions of the broad ion beam have an ion energy from 5 eV to 40k eV and a fluence from lxlO 10 ions/cm 2 to lxlO 21 ions/cm 2 .
- the irradiation time is from 1ms to 100s.
- the fracture toughness of the perforated sheet may be achieved by irradiatimg the perforated graphene sheet with a broad ion beam, wherein the ions of the broad ion beam have an ion energy from 50 eV to 1000 eV and a fluence from 3 x 10 10 ions/cm 2 to 8 x 10 11 ions/cm 2 .
- Other methods for dilating, reshaping and/or stabilizing the pores include, but are not limited to exposure to ultraviolet light and oxygen, use of a carbon-selective etching solution, and application of heat. Electron irradiation could also be applied with energies in the 10-300 keV range.
- the methods described herein may further comprise one or more of the following features.
- the sheet of graphene-based material or the sheet comprising a graphene-based material is heated.
- heating may add energy to the system.
- CTE coefficient of thermal expansion
- Suitable heating methods include, but are not limited to, Joule heating of the graphene-based material, IR radiation, heating via a conductive plate, or any combination of the above.
- the graphene layers are tilted relative to the incidence angle of the impinging Ps.
- this tilt is greater than zero and less than or equal to 89 degrees, is greater than 30 degrees and less than or equal to 89 degrees, or is from 45 degrees to 70 degrees.
- an incidence angle of collimated nanoparticles may be referenced normal to the basal plane of the top-most sheet of graphene or other material.
- a trace amount of gas or other material containing an element or moiety of interest for functionalization of pore edges is present before NP perforation, during NP perforation, after NP perforation or any combination thereof to functionalize pores produced by the NPs.
- the gas may be introduced on the front side, back side, or both sides of the sheet of graphene-based material.
- a trace amount of a gas is present during NP perforation and/or after NP perforation to etch pores produced by the NPs.
- the pressure of gas is less than 10 "3 Torr.
- the graphene-based material is pressurized with a gas from behind during exposure to the nanoparticle beam.
- the gas pressure strains the graphene-based material during perforation.
- the gas is used to functionalize the pores once the pores are produced.
- the preferred gases for before and during functionalization would depend on the reaction of graphene and the gas within the high energy environment of the particle impact. This would be within about 100 nm of the edge of the particle impact. This fits into two general classes, and the gases would be added at a partial pressure of from lxlO "6 Torr to lxl 0 "3 Torr.
- the first class would be species that reacts with radicals, carbanions (negative charge centered on a carbon) and carbocations (positive charge centered on a carbon). Representative molecules include carbon dioxide, ethylene oxide and isoprene.
- the second class would be species that fragment to create species that react with graphene and defective graphene. Representative molecules would be polyethylene glycol, diacytylperoxide, azobisisobutyronitrile, and phenyl diazonium iodide.
- the disclosure provides methods for perforating a graphene-containing sheet where a mask is used to limit perforation by the nanoparticles.
- the mask is placed "in front of the graphene layer(s) with respect to the source of nanoparticles.
- the mask includes openings and nanoparticle perforation preferentially occurs through openings in the mask.
- Exemplary masks include, but are not limited to, masks formed from self-assembled bead layers, masks formed by selective etching of block co-polymer layers, masks formed by soft landing of nanoparticles, masks of patterned metal or polymer layers and masks formed from perforated graphene.
- a polymeric photoresist can be used to make a patterned polymer layer via lithography.
- a patterned metal layer can serve as both a mask and as an electrode.
- a sacrificial deformation layer is placed "in front of the graphene layer(s) with respect to the source of nanoparticles.
- a deformation layer can be used to deform the nanoparticles, but still allow the nanoparticles to pass and continue on with sufficient energy to perforate the graphene layer(s).
- Exemplary materials for the sacrificial deformation layer include graphene or another two-dimensional material.
- the nanoparticles are deformed to assume an oblate configuration.
- the disclosure provides methods for perforating a composite sheet including at least one layer of graphene and at least one layer of another material. Additionally, the disclosure provides methods for perforating a sheet including a plurality of layers of graphene and at least one layer of another material. In examples, the layer of additional material is a contiguous layer or is not a contiguous layer. The sheet may be viewed as a composition of graphene and the other material(s).
- the methods involve exposing the composite sheet to a particle beam comprising nanoparticles (NPs) or clusters to perforate the stacked graphene sheets.
- the nanoparticle or cluster energy is greater than or equal to about 2 keV but less than about 500 keV, greater than 2 keV and less than 100 keV, greater than 2 keV and less than 50 keV or greater than or equal to 2 keV and less than or equal to 30 keV.
- the nanoparticle comprises a plurality of atoms and the energy is from 0.05 eV to 50 eV per atom or 0.1 eV to 50 eV per atom.
- the fluence is lxlO 8 - lxlO 12 Ps/cm 2 .
- the nanoparticles are from 1 nm to 50 nm, 2 nm to 50 nm, 1 nm to 25 nm, 2 nm to 25 nm, 2 nm to 10 nm, 3 nm to 30 nm or 10 nm to 50 nm in size.
- the nanoparticles are from 3 nm to 15 nm.
- the perforation methods for perforation of composite materials can incorporate additional features as previously described for nanoparticle perforation of graphene.
- the layers of the composite membranes can be tilted relative to the incidence angle of the impinging Ps.
- the graphene layer(s) are supported on a substrate and the at least one layer of the material other than graphene is "on top of of the graphene layer(s) and supported by the graphene layer(s).
- a layer or partial layer of graphene nanoplatelets is deposited on top of a graphene layer.
- a two- dimensional material having different biorelevant properties than graphene can be placed "in front" of the graphene layers.
- a two-dimensional material can be selected for its ease of modification with a desired functionalization or coating. Suitable two- dimensional materials for this example include, but are not limited to MoS 2 and h-BN.
- the layer of the other material is inserted between two graphene layers.
- the other material(s) can be added between the layers to aid in perforation, to give additional functionality to the composite or a combination thereof.
- Exemplary layers of material other than graphene include, but are not limited to, porous materials and spacer materials. Both types of material can limit or prevent contact between adjacent graphene layers and influence the elasticity of the composite, thereby influencing the nanoparticle perforation process.
- Exemplary porous materials include, but are not limited to, highly perforated 2D materials, such as graphene and carbon nanomembranes (C Ms), block co-polymer (BCP) layers (with one element removed to make it porous), patterned metal and inorganic layers, thin porous Si, Si0 2 , and SiN layers, irregularly shaped particles that may or may not have been fused to each other, and zeoloite particles.
- Exemplary spacer materials include, but are not limited to, carbon nanotubes and nanoparticles and lacy carbon.
- the other material is a 2D material other than graphene or a material that is typically unstable under perforation conditions (e.g. water).
- the added layers are located at the pore edges and provide functionalization to the pores.
- the disclosure provides methods for perforating a thin carbon-based material.
- Exemplary thin carbon based materials have a thickness from 0.5 nm to 10 nm and include, but are not limited to thin carbon nanomembranes and graphene nanoplatelet membranes.
- Carbon nanomembranes are typically generated from crosslinked aromatic self-assembled monolayers and can be approximately 1 nm thick (M. Ai and A. Golzhauser, Beilstein Bozen Symposium on Molecular Engineering and Control May 14th - 18th, 2012, Prien (Chiemsee), Germany).
- These Carbon nanomembranes (C M) are appropriate for being perforated.
- Further embodiments include combinations of these Carbon nanomembranes with graphene, such as layers arranged as graphene/C M (graphen on CNM), CNM/graphene (CNM on graphene), and graphene/CNM/graphene.
- the methods involve exposing the composite sheet to a particle beam comprising nanoparticles (NPs) or clusters to perforate such carbon-based materials.
- NPs nanoparticles
- the nanoparticle or cluster energy greater than or equal to about 2 keV but less than about 500 keV, greater than 2 keV and less than 100 keV, greater than 2 keV and less than 50 keV or greater than or equal to 2 keV and less than or equal to 30 keV.
- the nanoparticle comprises a plurality of atoms and the energy is from 0.05 eV to 50 eV per atom or 0.1 eV to 50 eV per atom.
- the fluence is lxlO 8 - lxlO 12 NPs/cm 2 .
- the nanoparticles are from 1 nm to 50 nm, 2 nm to 50 nm, 1 nm to 25 nm, 2 nm to 25 nm, 2 nm to 10 nm, 3 nm to 30 nm or 10 nm to 50 nm in size.
- the perforation methods for perforation of composite materials can incorporate additional features as previously described for nanoparticle perforation of graphene layers.
- the layers of the composite membranes which may be perforated can be tilted relative to the incidence angle of the impinging NPs.
- one or more cleaning methods is used to remove residual nanoparticles from the surface of the sheet of graphene-based material or the sheet comprising a graphene-based material.
- the cleaning methods may alternately or additionally remove material from substrate.
- an acid treatment can be suitable for removing residual metal nanoparticles.
- residual nanoparticles are not removed from the surface, but following perforation the residual particles are reacted with graphene, used to catalytically remove the graphene, used to rip graphene with magnetic pull on ferromagneticnanoparticles or evaporate the graphene via an
- the Ps introduce localized oxidation upon a local increase in temperature.
- Multi-layer graphene sheets and graphene-based materials comprising multilayer graphene having a plurality of pores penetrating through the stacked sheets are also described in the present disclosure.
- Such perforated multi-layer graphene sheets will also be referred to herein as "perforated graphene” "perforated graphene-based materials” or “perforated two dimensional materials.”
- the present disclosure further describes composite membranes comprising the perforated graphene-based materials described herein, the composite membranes comprising the perforated graphene-based materials described herein and a porous substrate.
- the disclosure provided herein also relates to 2D materials, combinations of layered 2D materials and composite membranes thereof.
- the perforations can be about 100 nm in size or less, 50 nm in size or less, 20 nm in size or less, 10 nm in size or less, or less than about 5 nm in size, particularly in a size range from 1 nm to 100 nm, 2 nm to about 50 nm, 2 nm to about 20 nm, 2 nm to about 10 nm or from about 2 nm to about 5 nm.
- the coefficient of variation of the pore size is 0.1 to 2 and the porosity is from 0.1% to 15%.
- the pores extend all the way through the stacked graphene sheets.
- perforated graphene and perforated graphene-based materials comprising multilayered graphene produced by the techniques described herein can be used in filtration applications.
- the size or size range of perforations is adapted to the intended application.
- the perforated graphene-based materials disclosed herein and composite membranes including the these perforated graphene based materials are useful for a number of filtration, separation and/or barrier applications including, but not limited to salt filtration, protein separation, viral clearance, immunoisolation, food and beverage filtration and clarification.
- FIG. 1 is a scanning transmission electron microscopy image demonstrating perforation through two independently stacked layers of graphene by nanoparticles.
- FIG. 2 is a scanning transmission electron microscopy image demonstrating perforation through bilayer graphene by nanoparticles.
- FIG. 3 is a scanning transmission electron microscopy image demonstrating perforation by a collimated nanoparticle beam at a non-zero angle with respect to the normal of the graphene-containing sheet.
- FIGS 4A and 4B show the porosity present in a graphene-containing sheet after nanoparticle perforation (FIG. 4A) and after nanoparticle perforation followed by ion beam irradiation (FIG. 4B).
- FiG. 5 is a scanning electrion microscopy image of two independently stacked layers of single layer graphene on a track etched polyimide substrate with approximately 460nm diameter pores perforated by AgNP particles.
- Graphene represents a form of carbon in which the carbon atoms reside within a single atomically thin sheet or a few layered sheets (e.g., about 20 or less) of fused six- membered rings forming an extended sp 2 -hybridized carbon planar lattice.
- Graphene- based materials include, but are not limited to, single layer graphene, multilayer graphene or interconnected single or multilayer graphene domains and combinations thereof.
- multilayer graphene includes 2 to 25 layers, 2 to 20 layers, 2 to 10 layers or 2 to 5 layers.
- layers of multilayered graphene are stacked, but are less ordered in the z direction (perpendicular to the basal plane) than a thin graphite crystal.
- graphene-based materials also include materials which have been formed by stacking single or multilayer graphene sheets.
- Multi-layered graphene as referred to herein includes multiple sheets of graphene formed by layering or stacking independently as-synthesized sheets on a substrate.
- independently as- synthesized sheets which have been layered or stacked on a substrate are termed
- independently stacked Adjacent graphene layers formed by independent stacking can be less ordered in the z direction than as-synthesized multilayer graphene. In examples, independently stacked adjacent layers do not display A-B, A-B-A or A-B-C-A stacking. In additional examples, there is no defined registry of adjacent layers of independently stacked graphene. Without wishing to be bound by any particular belief, structural differences between independently stacked multi-layer graphene and as-synthesized multilayer graphene are believed to contribute to differences in nanoparticle perforation behavior demonstrated in Example 1.
- layers of as-synthesized sheets of graphene which have been stacked in this fashion are less ordered in the z direction, i.e., the lattices of the sheets do not line up as well, than layers in an as-synthesized multilayer graphene sheet.
- Suitable as-synthesized sheets include sheets of single layer graphene (SLG), sheets of bi-layer graphene (BLG) or sheets of few layer graphene (FLG graphene, for example up to 5 layers of graphene).
- SSG single layer graphene
- BSG bi-layer graphene
- FLG graphene few layer graphene
- Another sheet of the SLG is then floated down on the already prepared SLG-substrate stack.
- This would now be 2 layers of "as-synthesized" SLG on top of the substrate.
- This can be extended to few layer graphene (FLG) or a mixture of SLG and FLG; and can be achieved through transfer methods known to the art.
- Other transfer methods are known to the art, including stamp methods.
- a polymer transfer method can be used to assemble the stack of polymer layers.
- a number of layers is intended to refer to that number of separate layers of transferred graphene.
- a layer of transferred graphene can have a range of graphene layers (e.g.
- the stack has a range of graphene layers. For example, if 5 layers of transferred graphene each have 1 to 5 layers, then regions where the 5 sheets line up with 5 layers, effectively have 25 layers of graphene there. Depending on the perforation conditions, the thicker regions of the stack may not perforate. In an embodiment, layering of different sheets of graphene results in a desirable membrane for filtration and separation applications.
- a sheet of graphene-based material is a sheet of single or multilayer graphene or a sheet comprising a plurality of interconnected single or multilayer graphene domains.
- the multilayer graphene domains have 2 to 5 layers or 2 to 10 layers.
- a "domain" refers to a region of a material where atoms are uniformly ordered into a crystal lattice. A domain is uniform within its boundaries, but different from a neighboring region.
- a single crystalline material has a single domain of ordered atoms.
- at least some of the graphene domains are nanocrystals, having domain size from 1 to 100 nm or 10-100 nm.
- the graphene domains have a domain size from 100 nm to 500 microns, 100 nm to 1 micron, or from 200 nm to 800 nm, or from 300 nm to 500 nm.
- a domain of multilayer graphene may overlap a neighboring domain. "Grain boundaries" formed by crystallographic defects at edges of each domain differentiate between neighboring crystal lattices.
- a first crystal lattice may be rotated relative to a second crystal lattice, by rotation about an axis perpendicular to the plane of a sheet, such that the two lattices differ in "crystal lattice orientation".
- the sheet of graphene-based material is a sheet of multilayer graphene or a combination of single and multilayer graphene.
- the sheet of graphene-based material is a sheet comprising a plurality of interconnected multilayer or single and multilayer graphene domains.
- interconnected domains are covalently bonded together to form the sheet.
- the sheet is polycrystalline.
- the thickness of the sheet of graphene-based material is from, 0.3 to 10 nm, from 0.3 to 5 nm, or from 0.3 to 3 nm. In an embodiment, the thickness includes both single layer graphene and the non-graphenic carbon.
- a sheet of graphene-based material comprises intrinsic or native defects.
- Intrinsic or native defects are those resulting from preparation of the graphene-based material in contrast to perforations which are selectively introduced into a sheet of graphene-based material or a sheet of graphene.
- Such intrinsic or native defects include, but are not limited to, lattice anomalies, pores, tears, cracks or wrinkles.
- Lattice anomalies can include, but are not limited to, carbon rings with other than 6 members (e.g. 5, 7 or 9 membered rings), vacancies, interstitial defects (including incorporation of non- carbon atoms in the lattice), and grain boundaries.
- perforations do not include openings in the graphene lattice due to intrinsic or native defects or grain boundaries.
- graphene is the dominant material in a graphene-based material.
- a graphene-based material comprises at least 20% graphene, 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% graphene.
- a graphene-based material comprises a range of graphene selected from 30% to 95%, or from 40% to 80% from 50% to 70%, from 60% to 95% or from 75%) to 100%.
- the amount of graphene in the graphene-based material is measured as an atomic percentage.
- a sheet of graphene-based material further comprises non- graphenic carbon-based material located on a surface of the sheet of graphene-based material.
- the sheet is defined by two base surfaces (e.g. top and bottom faces of the sheet) and side faces.
- the "bottom" face of the sheet is that face which contacted the substrate during growth of the sheet and the "free" face of the sheet opposite the "bottom” face.
- non-graphenic carbon-based material is located on a base surface of the sheet (e.g. the substrate side of the sheet and/or the free surface of the sheet).
- the sheet of graphene-based material includes a small amount of one or more other materials on the surface, such as, but not limited to, one or more dust particles or similar contaminants.
- the amount of non-graphenic carbon-based material is less than the amount of graphene.
- the surface coverage of the sheet of non- graphenic carbon-based material is greater than zero and less than 80%, from 5% to 80%, from 10%) to 80%, from 5% to 50% or from 10% to 50%. This surface coverage may be measured with transmission electron microscopy, which gives a projection.
- the amount of graphene in the graphene-based material is from 60% to 95% or from 75% to 100%.
- the non-graphenic carbon-based material does not possess long range order and may be classified as amorphous.
- the non-graphenic carbon-based material further comprises elements other than carbon and/or hydrocarbons.
- non-carbon elements which may be incorporated in the non-graphenic carbon include hydrogen, oxygen, silicon, copper and iron.
- the non-graphenic carbon-based material comprises hydrocarbons.
- carbon is the dominant material in non-graphenic carbon-based material.
- a non- graphenic carbon-based material comprises 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 at least 95% carbon.
- a non-graphenic carbon-based material comprises a range of carbon selected from 30% to 95%, or from 40% to 80%, or from 50% to 70%.
- the amount of carbon in the non-graphenic carbon-based material is measured as an atomic percentage.
- the sheet of graphene based material is larger than a flake which would be obtained by exfoliation.
- the sheet has a lateral dimension greater than about 1 micrometer.
- a lateral dimension is perpendicular to the thickness of the sheet.
- the term 'two-dimensional material' will refer to any extended planar structure of atomic thickness, including both single- and multi-layer variants thereof.
- Multi-layer two-dimensional materials can include up to about 20 stacked layers.
- a two-dimensional material suitable for the present structures and methods can be any substance having an extended planar molecular structure and an atomic level thickness.
- Particular examples of two-dimensional materials include graphene films, graphene-based material, transition metal dichalcogenides, metal oxides, metal hydroxides, graphene oxide, a-boron nitride, silicone, germanene, or other materials having a like planar structure.
- transition metal dichalcogenides include molybdenum disulfide and niobium diselenide.
- metal oxides include vanadium pentoxide.
- Graphene or graphene-based films according to the embodiments of the present disclosure can include single-layer or multi-layer films, or any combination thereof. Choice of a suitable two-dimensional material can be determined by a number of factors, including the chemical and physical environment into which the graphene, graphene-based material or other two-dimensional material is to be terminally deployed, ease of perforating the two-dimensional material, and the like.
- Nanomaterials in which pores are intentionally created will be referred to herein as "perforated graphene", “perforated graphene-based materials” or “perforated two- dimensional materials.”
- the size distribution of holes may be narrow, e.g., limited to 0.1 to 0.5 coefficient of variation.
- the characteristic dimension of the holes is selected for the application.
- the characteristic dimension is the diameter of the hole.
- the characteristic dimension can be taken as the largest distance spanning the hole, the smallest distance spanning the hole, the average of the largest and smallest distance spanning the hole, or an equivalent diameter based on the in-plane area of the pore.
- perforated graphene-based materials include materials in which non-carbon atoms have been incorporated at the edges of the pores.
- the pore is asymmetric with the pore size varying along the length of the hole (e.g. pore size wider at the free surface of the graphene-based material than at the substrate surface or vice versa).
- the pore size may be measured at one surface of the sheet of graphene based material.
- Quantitative image analysis of pore features may include measurement of the number, area, size and/or perimeter of pore features.
- a pore size distribution is obtained.
- the coefficient of variation of the pore size is calculated herein as the ratio of the standard deviation of the pore size to the mean of the pore size.
- the ratio of the area of the perforations to the ratio of the area of the sheet is used to characterize the sheet.
- the area of the perforations may be measured using quantitative image analysis.
- the area of the sheet may be taken as the planar area spanned by the sheet if it is desired to exclude the additional sheet surface area due to wrinkles or other non-planar features of the sheet.
- the present disclosure is directed, in part, to multi-layer graphene sheets and sheets of graphene-based material having about 2 to about 10 graphene sheets stacked upon one another and a plurality of pores penetrating through the stacked graphene sheets.
- the present disclosure is also directed, in part, to methods for perforating multi-layer graphene sheets and sheets of graphene-based material comprising multilayer graphene and defining pores therein that extend through the multiple graphene sheets.
- Perforated graphene i.e., graphene having a plurality of pores defined therein
- has a number of possible applications including, for example, use as a molecular filter, use as a barrier material, use as a defined band gap material, and use as an electrically conductive filler material with tunable electrical properties within polymer composites.
- perforated graphene there are few reliable techniques to reproducibly introduce a plurality of pores in graphene, where the pores are presented in a desired pore density and pore size. Generation of sub-nanometer pores can be particularly problematic.
- the pretreatment step for the graphene-based material is selected from thermal treatment, UV-oxygen treatment, ion beam treatment, and combinations thereof.
- thermal treatment includes heating to a temperature from 200 °C to 800 °C at a pressure of 10 "7 torr to atmospheric pressure for a time of 2 hours to 8 hours.
- UV-oxygen treatment involves exposure to light from 150 nm to 300 nm and an intensity from 10 to 100 mW/cm 2 at 6mm distance for a time from 60 to 1200 seconds.
- UV-oxygen treatment is performed at room temperature or at a temperature greater than room temperature.
- UV-oxygen treatment is performed at atmospheric pressure (e.g. 1 atm) or under vacuum.
- ion beam pretreatment involves exposure one or more of the graphene layers to ions having an ion energy from 50 eV to 1000 eV (for
- the fluence is from 3 x 10 10 ions/cm 2 to 8 x 10 11 ions/cm 2 or 3 x 10 10 ions/cm 2 to 1 x 10 14 ions/cm 2 (for pretreatment).
- the source of ions is collimated, such as a broad beam or flood source.
- the ions are noble gas ions such as Xe + .
- modifying the sheet of perforated graphene-based material comprises creating a second set pores having a second pore size extending through the multiple graphene sheets, modifying the first pores size or combinations thereof.
- one or more pretreatment steps are performed while the graphene-based material is attached to a substrate, such as a growth substrate.
- the metal growth substrate is a substantially continuous layer of metal rather than a grid or mesh.
- Metal growth substrates compatible with growth of graphene and graphene-based materials include transition metals and their alloys.
- the metal growth substrate is copper based or nickel based.
- the ion source provides a broad ion field.
- the source of ions may be an ion flood source.
- the ion flood source does not include focusing lenses.
- the ion source is operated at less than atmospheric pressure, such as at 10 "3 to 10 "5 torr or 10 "4 to 10 "6 torr. If perforation efficiency is lower than desired after one pretreatment step, an additional pretreatment step can be used before re-exposing the graphene layer(s) to nanoparticle or clusters.
- the particle beam is a nanoparticle beam or cluster beam.
- the beam is collimated or is not collimated.
- the beam need not be highly focused.
- a plurality of the nanoparticles or clusters is singly charged.
- nanoparticles comprise from 500 to 2,000,000 atoms, from 500 to 250,000 atoms or from 500 to 5,000 atoms.
- metal particles are suitable for use in the methods of the present disclosure.
- nanoparticles of Al, Ag, Au, Ti, Cu and nanoparticles comprising Al, Ag, Au, Ti, Cu are suitable.
- Metal Ps can be generated in a number of ways including magnetron sputtering and liquid metal ion sources (LMIS). Methods for generation of nanoparticles are further described in Cassidy, Cathal, et al. "Inoculation of silicon nanoparticles with silver atoms.” Scientific reports 3 (2013), Haberland, Hellmut, et al.
- Gas cluster beams can be made when high pressure gas adiabatically expands in a vacuum and cools such that it condenses into clusters.
- Clusters can also be made ex situ such as C 6 o and then accelerated towards the graphene.
- the nanoparticles are specially selected to introduce moieties into the graphene.
- the nanoparticles function as catalysts.
- the moieties may be introduced at elevated temperatures, optionally in the presence of a gas.
- the nanoparticles introduce "chiseling" moieties, which are moieties that help reduce the amount of energy needed to remove an atom during irradiation.
- the size of the perforation apertures is controlled by controlling both the nanoparticle size and the nanoparticle energy. Without wishing to be bound by any particular belief, if all the nanoparticles have sufficient energy to perforate, then the resulting perforation is believed to correlated with the nanoparticle sizes selected.
- the size of the perforation is believed to be influenced by deformation of the nanoparticle during the perforation process. This deformation is believed to be influenced by both the energy and size of the nanoparticle and the stiffness of the graphene layer(s). A grazing angle of incidence of the nanoparticles can also produce deformation of the nanoparticles. In addition, if the nanoparticle energy is controlled, it is believed that nanoparticles can be deposited with a large mass and size distribution, but that a sharp cutoff can still be achieved.
- the mechanism of perforation is believed to be a continuum bound by sputtering on one end (where enough energy is delivered to the graphene sheet to atomize the carbon in and around the NP impact site) and ripping or fracturing (where strain induced failure opens a torn hole but leaves the graphene carbons as part of the original sheet).
- Part of the graphene layer may fold over at the site of the rip or fracture.
- the cluster can be reactive so as to aid in the removal of carbon (e.g. an oxygen cluster or having trace amounts of a molecule known to etch carbon in a gas cluster beam i.e. a mixed gas cluster beam).
- the stiffness of a graphene layer is believed to be influenced by both the elastic modulus of graphene and the tautness of the graphene.
- Factors influencing the elastic modulus of a graphene layer are believed to include temperature, defects (either small defects or larger defects from P irradiation), physisorption, chemisorption and doping.
- Tautness is believed to be influenced by coefficient of thermal expansion mismatches (e.g. between substrate and graphene layer) during deposition, strain in the graphene layer, wrinkling of the graphene layer.
- strain in a graphene layer can be influenced by a number of factors including application of gas pressure to the backside (substrate side) of a graphene layer, straining of an elastic substrate prior to deposition of graphene, flexing of the substrate during deposition, and defecting the graphene layer in controlled regions to cause the layer to locally contract and increase the local strain.
- nanoparticle perforation can be further controlled by straining the graphene layers during perforation to induce fracture, thereby "ripping" or “tearing" one or more graphene layers.
- the stress is directional and used to preferentially fracture in a specific orientation. For example, ripping of one or more graphene sheets can be used to create "slit" shaped apertures; such apertures can be substantially larger than the nanoparticle used to initiate the aperture.
- the stress is not oriented in a particular direction.
- the pores are functionalized.
- the pores are functionalized by exposure to gas during and/or following the perforation process.
- the exposure to gas may occur at temperatures above room temperature.
- the pores can have more than one effective functionalization.
- a thin layer of a functionalizing moiety is applied to the surface before NP perforation, during NP perforation and after NP perforation.
- the thin layer may be formed by applying a fluid to the surface.
- the gas pressure is 10 "4 Torr to atmospheric pressure.
- functionalizing moieties include, but are not limited to water, water vapor, polyethylene glycol, oxygen, nitrogen, amines, caboxycylic acid.
- the preferred gasses for before and during functionalization would depend on the reaction of graphene and the gas within the high energy environment of the particle impact. This would be within about 100 nm of the edge of the particle impact. This fits into two general classes, and the gases would be added at a partial pressure of from lxlO "6 Torr to lxl 0 "3 Torr.
- the first class would be species that reacts with radicals, carbanions (negative charge centered on a carbon) and carbocations (positive charge centered on a carbon). Representative molecules include carbon dioxide, ethylene oxide and isoprene.
- the second class would be species that fragment to create species that react with graphene and defective graphene. Representative molecules would be polyethylene glycol, diacytylperoxide, azobisisobutyronitrile, and phenyl diazonium iodide.
- a sheet of graphene-based material is perforated to create a first set of perforations, the first set of perforations are functionalized with a first moeity, the sheet is reperforated to create a second set of perforations, and the second set of perforations is functionalized with a second moiety.
- the multi-layer graphene contains between about 2 stacked graphene sheets and about 20 stacked graphene sheets according to the various embodiments of the present disclosure. Too few graphene sheets can lead to difficulties in handling the graphene as well as an increased incidence of intrinsic graphene defects. Having more than about 20 stacked graphene sheets, in contrast, can make it difficult to perforate all of the graphene sheets.
- the multilayer sheets may be made by individually growing sheets and making multiple transfers to the same substrate.
- the multi-layer graphene perforated by the techniques described herein can have 2 graphene sheets, or 3 graphene sheets, or 4 graphene sheets, or 5 graphene sheets, or 6 graphene sheets, or 7 graphene sheets, or 8 graphene sheets, or 9 graphene sheets, or 10 graphene sheets, or 11 graphene sheets, or 12 graphene sheets, or 13 graphene sheets, or 14 graphene sheets, or 15 graphene sheets, or 16 graphene sheets, or 17 graphene sheets, or 18 graphene sheets, or 19 graphene sheets, or 20 graphene sheets. Any subrange between 2 and 20 graphene sheets is also contemplated by the present disclosure.
- perforated graphene produced by the techniques described herein can be used in filtration processes.
- the perforated graphene produced by the techniques described herein can be utilized in fields such as, for example, advanced sensors, batteries and other electrical storage devices, and semiconductor devices.
- the perforated graphene can be placed upon a porous polymer substrate after being perforated.
- the combination of the porous polymer substrate and the graphene can constitute a filter in various embodiments, such as a reverse osmosis filter or a nanofiltration filter. Suitable porous polymer substrates are not believed to be particularly limited.
- FIG. 1 is a transmission electron microscopy image demonstrating perforation through two independently stacked layers of graphene by nanoparticles.
- Two layers of CVD graphene material were prepared. Each layer received ion beam treatment on Cu growth substrate, transfer to lacey carbon TEM grid, UV-oxygen treatment and 300°C bakeout for 8 hours before the layers were stacked. The stacked layers were exposed to 6.5kV Ag nanoparticles (NP). The P distribution was centered on 6nm and the fluence was approximately 5xl0 10 Ps /cm 2 .
- FIG. 2 is a transmission electron microscopy image demonstrating perforation through bilayer graphene by nanoparticles.
- the CVD graphene was prepared then received ion beam treatment on Cu substrate, was transferred to lacey carbon TEM grid, received UV-oxygen treatment and 300°C bakeout for 8 hours.
- the graphene was exposed to 7.5kV AgNP with NP distribution centered on 6nm at a fluence of approximately 5xlO u NPs/cm 2 , followed by a 24 hourr bake at 300° C in Ar with slow cool down.
- EXAMPLE 2 Nanoparticle Perforation at an Angle other than Ninety Degrees with Respect to a Sheet of with Two Stacked Graphene Layers
- FIG. 3 is a transmission electron microscopy image of perforations through two stacked layers of graphene made by exposure to a particle beam comprising nanoparticles.
- the nanoparticles were provided at an incidence angle of approximately greater than 45 degrees to the normal of the basal plane of the sheet of graphene material.
- the NPs were of 9-1 lnm diameter at an energy of 30keV.
- the pores were typically 10-12 nm at their base, and varied in length from about 20nm to 70mm. The pore size was larger than that obtained for nanoparticle perforation approximately normal to the basal sheet of graphene material under similar nanoparticle size, energy and fluence conditions. In addition, some evidence of ripping was observed on the top graphene surface.
- FIGS 4A and 4B illustrate a sheet of graphene based material after nanoparticle perforation (FIG. 4A) and after subsequent ion beam irradiation (FIG. 4B).
- the material was two layers of independently stacked graphene.
- the perforation conditions were 7-10nm NPs at 12 keV.
- the ion beam irradiation conditions were Xe+ at 300V with 2E 14 Xe+/cm 2 fluence and 3E 14 Xe+/cm 2 /s flux.
- the porousity went from 5% to 14%.
- FiG. 5 is a scanning electrion microscopy image of two independently stacked layers of single layer graphene on on a track etched polyimide substrate with approximately 460nm diameter pores perforated by AgNP particles.
- TEPI 460/25) is track etched polyimide that has an average pore diameter (of individual, non overlapping pores) on the side that graphene is applied to it of 460nm and is approximately 25um thick.
- the perforation conditions were 10-15nm AgNP particles at 30keV.
Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201562202122P | 2015-08-06 | 2015-08-06 | |
PCT/US2016/027610 WO2017023377A1 (en) | 2015-08-06 | 2016-04-14 | Nanoparticle modification and perforation of graphene |
Publications (2)
Publication Number | Publication Date |
---|---|
EP3331824A1 true EP3331824A1 (en) | 2018-06-13 |
EP3331824A4 EP3331824A4 (en) | 2019-05-22 |
Family
ID=62079091
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP16833430.8A Withdrawn EP3331824A4 (en) | 2015-08-06 | 2016-04-14 | Nanoparticle modification and perforation of graphene |
Country Status (2)
Country | Link |
---|---|
EP (1) | EP3331824A4 (en) |
CN (1) | CN108025279A (en) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108724867B (en) * | 2018-06-06 | 2020-05-19 | 合肥工业大学 | Porous graphene driver with double stimulus sources responding, preparation method and application |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU2013231930B2 (en) * | 2012-03-15 | 2017-05-25 | King Fahd University Of Petroleum & Minerals | Graphene based filter |
WO2014159043A1 (en) * | 2013-03-13 | 2014-10-02 | Lockheed Martin Corporation | Nanoporous membranes and methods for making the same |
-
2016
- 2016-04-14 EP EP16833430.8A patent/EP3331824A4/en not_active Withdrawn
- 2016-04-14 CN CN201680053191.5A patent/CN108025279A/en active Pending
Also Published As
Publication number | Publication date |
---|---|
CN108025279A (en) | 2018-05-11 |
EP3331824A4 (en) | 2019-05-22 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10696554B2 (en) | Nanoparticle modification and perforation of graphene | |
US9744617B2 (en) | Methods for perforating multi-layer graphene through ion bombardment | |
US9870895B2 (en) | Methods for perforating two-dimensional materials using a broad ion field | |
US20160009049A1 (en) | Nanoporous membranes and methods for making the same | |
US10981120B2 (en) | Selective interfacial mitigation of graphene defects | |
AU2013235643B2 (en) | Methods for perforating graphene using an activated gas stream and perforated graphene produced therefrom | |
US10203295B2 (en) | Methods for in situ monitoring and control of defect formation or healing | |
Ochedowski et al. | Nanostructuring graphene by dense electronic excitation | |
US10418143B2 (en) | Perforatable sheets of graphene-based material | |
JP2010212619A (en) | Graphene manufacturing method, graphene, graphene manufacturing device, and semiconductor device | |
US20170036911A1 (en) | Perforated sheets of graphene-based material | |
US20170296982A1 (en) | Healing of thin graphenic-based membranes via charged particle irradiation | |
EP3331824A1 (en) | Nanoparticle modification and perforation of graphene | |
WO2017049236A1 (en) | Nanoporous membranes and methods for making the same | |
EP3331644A1 (en) | Perforatable sheets of graphene-based material |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE |
|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE |
|
17P | Request for examination filed |
Effective date: 20180306 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR |
|
AX | Request for extension of the european patent |
Extension state: BA ME |
|
DAV | Request for validation of the european patent (deleted) | ||
DAX | Request for extension of the european patent (deleted) | ||
A4 | Supplementary search report drawn up and despatched |
Effective date: 20190425 |
|
RIC1 | Information provided on ipc code assigned before grant |
Ipc: B01D 67/00 20060101ALI20190417BHEP Ipc: C01B 32/182 20170101AFI20190417BHEP Ipc: B01D 71/02 20060101ALI20190417BHEP Ipc: C01B 32/194 20170101ALI20190417BHEP |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN |
|
18D | Application deemed to be withdrawn |
Effective date: 20211103 |