# Patent

## Title
Methods for perforating multi-layer graphene through ion bombardment

## Abstract

Multi-layer sheets of graphene-based material having a plurality of pores extending therethrough are described herein. Methods for making the sheets include exposing a graphene-based material comprising multilayer graphene having from 5 to 20 layers of graphene to a particle beam having an ion energy of at least about 1500 eV to create damage tracks in the graphene sheets. The damage tracks in the graphene sheets are then exposed to a chemical etchant, such as an oxidant to define pores through the stacked graphene sheets. Production of the damage tracks and etching of the damage tracks can take place while the graphene is disposed on a substrate.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of priority under 35 U.S.C. §119 from U.S. Provisional Patent Application No. 62/039,856, filed Aug. 20, 2014, and is a continuation-in-part of U.S. patent application Ser. No. 14/610,770, filed Jan. 30, 2015, which claims the benefit of priority under 35 U.S.C. §119 to U.S. Provisional Patent Application No. 61/934,530, filed Jan. 31, 2014, each of which are hereby incorporated by reference in its entirety.


STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
FIELD
The present disclosure generally relates to graphene based materials and other two-dimensional materials, and, more specifically, to methods for producing pores in multi-layer stacked graphene sheets and other two-dimensional materials.
BACKGROUND
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. Although pristine graphene typically displays the highest electrical conductivity values, it can sometimes be desirable to tune the electrical conductivity and adjust the band gap. Tailoring of the band gap 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 gap can be influenced by both the size and number of holes present. Applications that have been proposed for graphene include optical devices, mechanical structures, and electronic devices. In addition to the foregoing applications, there has been some interest in perforated graphene for filtration applications, particularly single-layer perforated graphene.
Current techniques used to perforate CVD graphene include oxidation processes (e.g., UV ozone, plasma oxidation, and high temperatures), ion beams, template cutting (e.g., “cookie cutter” mechanical perforation), and direct synthesis using specialized growth substrates. However, these techniques are not presently suitable for large scale production of perforated graphene in commercially realistic quantities. Control of the pore size distribution and the number of pores per unit area can also be an issue. Production of sub-nanometer pores (<1 nm in pore size) can be particularly difficult to achieve.
Other two-dimensional materials having a thickness of a few nanometers or less and an extended planar lattice are also of interest for various applications. In an embodiment, a two dimensional material has a thickness of 0.3 to 1.2 nm. In other embodiment, a two dimensional material has a thickness of 0.3 to 3 nm. For example, 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.
In view of the foregoing, techniques that allow pores to be produced in graphene with a desired pore density and pore size would be of considerable benefit in the art. The present disclosure satisfies this need and provides related advantages as well.
SUMMARY
The present disclosure describes methods for introducing pores into the basal plane of a plurality of graphene sheets stacked upon one another. In embodiments, the methods involve exposing about 5-20 layers of stacked graphene sheets (i.e., multi-layer graphene) to a particle beam having an ion energy of about 1500 eV or greater (per ion) to produce damage tracks in the basal planes of the stacked graphene sheets. In further embodiments, the ion energy greater than about 1500 eV but less than about 10000 eV or greater than 1.5 keV and less than 100 keV. The present disclosure further describes perforation methods including the step of exposing a sheet of graphene-based material to an ion beam, the graphene-based material comprising multilayer graphene having from 5 to 20 layers of graphene.
In embodiments, the damage tracks extend through the multi-layer graphene. Thereafter, the damaged graphene sheets are exposed to a chemical etchant, such as an oxidant, that selectively attacks defects (e.g. triple carbon-carbon bonds) in the damage tracks to remove graphene-based carbon atoms within the damage tracks. The damage tracks are tunable in size based upon the ion and energy used. In an embodiment, the oxidant is selected from the group consisting of ozone, an aqueous solution of potassium permanganate, an aqueous solution of potassium permanganate and sulfuric acid, an aqueous solution of potassium permanganate and potassium hydroxide or a solution of hydrogen peroxide and sulfuric acid
In embodiments, the ion bombardment takes place while the graphene-based material is disposed on a substrate. In some embodiments, the bombardment and etching can take place while the graphene is disposed on a substrate. In embodiments, the substrate is a metal growth substrate or other substrate.
Multi-layer graphene sheets and graphene-based materials comprising multi-layer 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,” In some embodiments, the perforations can be about 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 about 0.2 nm to about 50 nm, 0.2 nm to about 20 nm, 0.2 nm to about 10 nm or from about 0.2 nm to about 5 nm. In embodiments, about 5 to about 20 stacked graphene sheets are present in the multi-layer graphene. In an embodiment, after perforation of the sheet the structure of the graphene based material in unperforated regions of the sheet is similar to that of the starting unperforated graphene based material.
In some embodiments, 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. Some of the pore size ranges describe herein are suitable for reverse osmosis filtration and molecular filtration applications.
The foregoing has outlined rather broadly the features of the present disclosure in order that the detailed description that follows can be better understood. Additional features and advantages of the disclosure will be described hereinafter. These and other advantages and features will become more apparent from the following description.



BRIEF DESCRIPTION OF THE DRAWINGS
For a more complete understanding of the present disclosure, and the advantages thereof, reference is now made to the following descriptions to be taken in conjunction with the accompanying drawings describing specific embodiments of the disclosure, wherein:
FIG. 1 shows an illustrative schematic demonstrating how pores can be selectively introduced into a plurality of stacked graphene sheets according to the techniques of the present disclosure; and
FIG. 2 shows an illustrative image of a perforated multi-layer graphene produced by the techniques of the present disclosure.



DETAILED DESCRIPTION
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 sp2-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. In embodiments, multilayer graphene includes 2 to 20 layers, 2 to 10 layers or 2 to 5 layers. In an embodiment, layers of multilayered graphene are stacked, but are less ordered in the z direction (perpendicular to the basal plane) than a thin graphite crystal.
In an embodiment, graphene-based materials also include materials which have been formed by stacking single or multilayer graphene sheets. For example, a sheet of single layer graphene (SLG) is layered via float-down on top of a substrate. Another sheet of the SLG is then floated it down on the already prepared SLG-substrate stack. This would now be 2 layers of “as synthesized” SLG on top of the substrate. This could be extended to few layer graphene (FLG) or a mixture of SLG and FLG; and could be achieved through transfer methods known to the art.
In an embodiment, 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. In embodiments, the multilayer graphene domains have 2 to 5 layers or 2 to 10 layers. As used herein, 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. For example, a single crystalline material has a single domain of ordered atoms. In an embodiment, at least some of the graphene domains are nanocrystals, having domain size from 1 to 100 nm or 10-100 nm. In an embodiment, at least some of the graphene domains have a domain size greater than 100 nm to 1 micron, or from 200 nm to 800 nm, or from 300 nm to 500 nm. In an embodiment, 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. In some embodiments, 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”.
In an embodiment, the sheet of graphene-based material is a sheet of multilayer graphene or a combination of single and multilayer graphene. In another embodiment, the sheet of graphene-based material is a sheet comprising a plurality of interconnected multilayer or single and multilayer graphene domains. In an embodiment, the interconnected domains are covalently bonded together to form the sheet. When the domains in a sheet differ in crystal lattice orientation, the sheet is polycrystalline.
In embodiments, the thickness of the sheet of graphene-based material is from 0.3 to 10 nm, 0.34 to 10 nm, from 0.34 to 5 nm, or from 0.34 to 3 nm. In an embodiment, the thickness includes both single layer graphene and the non-graphenic carbon.
In an embodiment, a sheet of graphene-based material comprises intrinsic defects. Intrinsic 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 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. As used herein, perforations do not include openings in the graphene lattice due to intrinsic defects or grain boundaries.
In embodiments, graphene is the dominant material in a graphene-based material. For example, 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. In embodiments, 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%. In an embodiment, the amount of graphene in the graphene-based material is measured as an atomic percentage.
In an embodiment, a sheet of graphene-based material further comprises non-graphenic carbon-based material located on a surface of the sheet of graphene-based material. In an embodiment, the sheet is defined by two base surfaces (e.g. top and bottom faces of the sheet) and side faces. In a further embodiment, 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. In an embodiment, 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). In a further embodiment, 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.
In an embodiment, the amount of non-graphenic carbon-based material is less than the amount of graphene. In embodiments, 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. In embodiments, the amount of graphene in the graphene-based material is from 60% to 95% or from 75% to 100%.
In an embodiment, the non-graphenic carbon-based material does not possess long range order and may be classified as amorphous. In embodiments, the non-graphenic carbon-based material further comprises elements other than carbon and/or hydrocarbons. In an embodiment, non-carbon elements which may be incorporated in the non-graphenic carbon include hydrogen, oxygen, silicon, copper and iron. In further embodiment, the non-graphenic carbon-based material comprises hydrocarbons. In embodiments, carbon is the dominant material in non-graphenic carbon-based material. For example, 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. In embodiments, 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%. In an embodiment, the amount of carbon in the non-graphenic carbon-based material is measured as an atomic percentage.
In further embodiments, the sheet of graphene based material is larger than a flake which would be obtained by exfoliation. For example, the sheet has a lateral dimension greater than about 1 micrometer. As used herein, a lateral dimension is perpendicular to the thickness of the sheet.
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. In an embodiment, the characteristic dimension of the holes is selected for the application. For circular holes, the characteristic dimension is the diameter of the hole. In embodiments relevant to non-circular pores, 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. As used herein, perforated graphene-based materials include materials in which non-carbon atoms have been incorporated at the edges of the pores. In embodiments, 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. In an embodiment, 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. In an embodiment, the equivalent diameter of each pore is calculated from the equation A=πd2/4. When the pore area is plotted as a function of equivalent pore diameter, 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.
In an embodiment, 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. In a further embodiment, characterization may be based on the ratio of the area of the perforations to the sheet area excluding features such as surface debris. In embodiments, the perforated area comprises 0.1% or greater, 1% or greater or 5% or greater of the sheet area, less than 10% of the sheet area, less than 15% of the sheet area, from 0.1% to 15% of the sheet area, from 1% to 15% of the sheet area, from 5% to 15% of the sheet area or from 1% to 10% of the sheet area. In a further embodiment, the perforations are located over greater than 10% or greater than 15% of said area of said sheet of graphene-based material.
The present disclosure is directed, in part, to multi-layer graphene sheets and sheets of graphene-based material having about 5 to about 20 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 defined band gap material, and use as an electrically conductive filler material with tunable electrical properties within polymer composites. Although a number of potential uses for perforated graphene exist, 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.
In the embodiments described herein, pore generation can desirably be controlled through modulation of the energy and nature of ions used for bombarding multi-layer graphene. In particular, the methods described herein involve exposing a multi-layer graphene having about 5-20 stacked graphene sheets to a particle beam (ion current) having an ion energy of 1500 eV or greater. In some embodiments, the ions can have an energy greater than about 1500 eV but less than about 10000 eV or greater than 1.5 keV and less than 100 keV. In embodiments, the ion source provides an ion dose to the multilayered material ranging from 1×1010 ions/cm2 to 1×1017 ions/cm2, from 1×1011 ions/cm2 to 1×1015 ions/cm2 or from 1×1013 ions/cm2 to 1×1019 ions/cm2. In an embodiment, the ion dose is adjusted based on the ion, with lighter ions (lower mass ions) being provided at a higher dosage. In embodiments, the ion flux or beam current density ranges from 0.1 nA/mm2 to 100 nA/mm2, from 0.1 nA/mm2 to 10 nA/mm2, 0.1 nA/mm2 to 1 nA/mm2, from 1 nA/mm2 to 10 nA/mm2, or from 10 nA/mm2 to 100 nA/mm2.
In embodiments of the present disclosure the particle beam provides a broad ion field. The source of the particle beam may be an ion flood source. In an embodiment, the ion flood source does not include focusing lenses. In embodiments, 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.
In embodiments, the interaction of the ions with the graphene sheets creates damage tracks in the basal plane of the stacked graphene sheets. The damage tracks extend through the stacked graphene sheets. Thereafter, the damaged graphene is exposed to a chemical etchant, such as an oxidant, to react defects such as carbon-carbon triple bonds with the oxidant to remove the graphene-based carbon atoms from the damage tracks but not the undamaged graphene adjacent thereto. Illustrative chemical etchants include oxidants such as, for example, ozone, potassium permanganate, sulfuric acid and combinations thereof and modified Hummer's solution. In an embodiment, the oxidant combines NaNO3, H2SO4 and KMnO4. Other strong oxidants may also be suitable and will be recognized by one having ordinary skill in the art. An exemplary etch time is 0.1 to 1 hr at room temperature. In an embodiment, these conditions are suitable for 0.1% modified Hummer's solution.
In embodiments, the pores are functionalized. In some embodiments, the pores are functionalized with oxygen moieties. For example, the etching process may be selected to achieve such functionalization. Subsequently, the oxygen functionalities can be reacted via a chemistry that converts the oxygenated functionalities. In additional embodiments, the pores are functionalized moieties comprising oxygen, nitrogen, phosphorus, sulfur, fluorine, chlorine, bromide, iodine or combinations thereof. In further embodiments, the pores are functionalized with moieties comprising boron, hydrogen, lithium, magnesium, aluminum or combinations thereof. In embodiments, the moieties may be charged moieties, hydrophobic moieties, or hydrophilic moieties. Functionalization may be covalent and/or non-covalent. Various methods for functionalization of graphene are known to the art. For example, Functionalization of Graphene, V. Georgakilis (ed.), Wiley, June 2014 and Chemical Functionalization of Carbon Nanomaterials: Chemistry and Applications, V. Thakur and M. Thakur (eds.), CRC Press, 2015 provide some description of functionalization of graphene and are incorporated herein by reference for description of graphene functionalization methods.
In embodiments, it is desirable and advantageous to perforate multiple graphene sheets at one time rather than perforating single graphene sheets individually, since multi-layer graphene is more robust and less prone to the presence of intrinsic defects than is single-layer graphene. In addition, the process is stepwise efficient, since perforated single-layer graphene can optionally be produced by exfoliating the multi-layer graphene after the pore definition process is completed. The pore size is also tailorable in the processes described herein, since the damage tracks produced by the ion beam are dependent upon the chosen ion and its energy. Thus, the processes described herein are desirable in terms of the number, size and size distribution of pores produced.
The multi-layer graphene contains between about 5 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 with the ion beam. In an embodiment, the multilayer sheets may be made by individually growing sheets and making multiple transfers to the same substrate. The processes described herein are not believed to be suitable for directly producing single-layer graphene, since the processes described herein directly produce perforated multi-layer graphene. In various embodiments, the multi-layer graphene perforated by the techniques described herein can have 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 5 and 20 graphene sheets is also contemplated by the present disclosure.
In various embodiments, the perforated graphene can have pores ranging between about 0.1 nm to about 10 nm in size or from about 0.2 nm to about 2.5 nm in size, as measured carbon center-to-carbon center, which can be desirable for utilization of this material in some filtration applications. In additional embodiments, the pores can range between about 0.2 nm to about 2 nm in size, or from about 0.5 nm to about 1.5 nm in size. In further embodiments, the pores range from 0.3 nm to 50 nm, 0.3 nm to 20 nm, 0.3 nm to 10 nm, 0.5 nm to 2.5 nm, 0.3 nm to 0.5 nm, 0.5 nm to 10 nm, or 5 nm to 20 nm. The pores extend all the way through the stacked graphene sheets.
The ions forming the particle beam can be used to tailor the size of the damage tracks produced upon bombarding the multi-layer graphene. Both the identity of the ions and their energy can influence the size of the damage tracks. In some embodiments, the ions are noble gas ions (ion of an element from Group 18 of the periodic table) or are selected from the group consisting of Xe+ ions, Ne+ ions, or Ar+ ions, In some embodiments, the ions can be xenon ions. In other illustrative embodiments, organic ions or organometallic ions such as tropyllium ions C7H7+ and ferrocenium ions (C5H5)2Fe+ can be used. In an embodiment, the organic or organometallic ion has an aromatic component. In an embodiment, the molecular mass of the organic ion or organometallic ion is from 75 to 200 or 90 to 200. The ions can strike the surface at any angle relative to the graphene basal plane, including normal to the basal plane of the top-most graphene sheet.
In some embodiments, the graphene-based material comprising multi-layer graphene is perforated while attached to a substrate. In an embodiment, the substrate is substantially nonporous, so that the graphene based material is supported rather than suspended. In some embodiments the substrate is a growth substrate while in other embodiments the substrate is a secondary substrate to which the graphene-based material is transferred after growth. In an embodiment, the substrate disperses an impact energy of the ions and/or neutralized ions with the substrate into an area of the graphene-based material surrounding the defects created upon interacting the ions and/or neutralized ions with the graphene and promotes expansion of the defects into holes.
In some embodiments, the graphene-based material comprising multi-layer graphene can be perforated while still on its growth substrate, such as a copper substrate. In an embodiment, the growth substrate is a metal growth substrate. In an embodiment, 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. In embodiments, the metal growth substrate is copper based or nickel based. Specifically, the damage tracks can be produced in the graphene enhanced by the substrate and then opened with the etchant. Thereafter, the graphene can be removed from the growth substrate (e.g., by ammonium persulfate etching) and transferred to a secondary substrate, such as a porous polymer or an inorganic membrane. Optionally, the graphene can be removed from the growth substrate before expanding the damage tracks or at the same time as expanding the damage tracks. Again, the greater stability of multi-layer graphene offers considerable flexibility in both the nature of the graphene product and how it is produced. The presence of the graphene on the substrate can also enhance the perforation and etching process.
In some embodiments, perforated graphene produced by the techniques described herein can be used in filtration processes. In addition, 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.
In some embodiments, 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. Suitable porous polymer substrates are not believed to be particularly limited.
FIG. 1 shows an illustrative schematic demonstrating how pores can be selectively introduced into a plurality of stacked graphene sheets according to the processes of the present disclosure. As shown in FIG. 1, a multi-layer graphene is exposed to an ion beam to produce a damage track therein. Thereafter, the carbon atoms in the damage track are removed by selective chemical etching to produce the perforated graphene having pores defined therethrough. Subsequently, the graphene can be removed from a substrate (not shown). FIG. 2 shows an illustrative microscopy image of a perforated multi-layer graphene produced by the techniques of the present disclosure.
Although the disclosure has been described with reference to the disclosed embodiments, one having ordinary skill in the art will readily appreciate that these are only illustrative of the disclosure. It should be understood that various modifications can be made without departing from the spirit of the disclosure. The disclosure can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the disclosure. Additionally, while various embodiments of the disclosure have been described, it is to be understood that aspects of the disclosure may include only some of the described embodiments. Accordingly, the disclosure is not to be seen as limited by the foregoing description.
Every formulation or combination of components described or exemplified can be used to practice the invention, unless otherwise stated. Specific names of compounds are intended to be exemplary, as it is known that one of ordinary skill in the art can name the same compounds differently. When a compound is described herein such that a particular isomer or enantiomer of the compound is not specified, for example, in a formula or in a chemical name, that description is intended to include each isomers and enantiomer of the compound described individual or in any combination. One of ordinary skill in the art will appreciate that methods, device elements, starting materials and synthetic methods other than those specifically exemplified can be employed in the practice of the invention without resort to undue experimentation. All art-known functional equivalents, of any such methods, device elements, starting materials and synthetic methods are intended to be included in this invention. Whenever a range is given in the specification, for example, a temperature range, a time range, or a composition range, all intermediate ranges and subranges, as well as all individual values included in the ranges given are intended to be included in the disclosure. When a Markush group or other grouping is used herein, all individual members of the group and all combinations and subcombinations possible of the group are intended to be individually included in the disclosure.
As used herein, “comprising” is synonymous with “including,” “containing,” or “characterized by,” and is inclusive or open-ended and does not exclude additional, unrecited elements or method steps. As used herein, “consisting of” excludes any element, step, or ingredient not specified in the claim element. As used herein, “consisting essentially of” does not exclude materials or steps that do not materially affect the basic and novel characteristics of the claim. Any recitation herein of the term “comprising”, particularly in a description of components of a composition or in a description of elements of a device, is understood to encompass those compositions and methods consisting essentially of and consisting of the recited components or elements. The invention illustratively described herein suitably may be practiced in the absence of any element or elements, limitation or limitations which is not specifically disclosed herein.
The terms and expressions which have been employed are used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the concepts herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention as defined by the appended claims.
In general the terms and phrases used herein have their art-recognized meaning, which can be found by reference to standard texts, journal references and contexts known to those skilled in the art. The preceding definitions are provided to clarify their specific use in the context of the invention.
All references throughout this application, for example patent documents including issued or granted patents or equivalents; patent application publications; and non-patent literature documents or other source material; are hereby incorporated by reference herein in their entireties, as though individually incorporated by reference, to the extent each reference is at least partially not inconsistent with the disclosure in this application (for example, a reference that is partially inconsistent is incorporated by reference except for the partially inconsistent portion of the reference).
All patents and publications mentioned in the specification are indicative of the levels of skill of those skilled in the art to which the invention pertains. References cited herein are incorporated by reference herein in their entirety to indicate the state of the art, in some cases as of their filing date, and it is intended that this information can be employed herein, if needed, to exclude (for example, to disclaim) specific embodiments that are in the prior art. For example, when a compound is claimed, it should be understood that compounds known in the prior art, including certain compounds disclosed in the references disclosed herein (particularly in referenced patent documents), are not intended to be included in the claims.

## Claims

1. A method comprising:
providing a sheet of graphene-based material comprising multi-layer graphene having between about 10 and about 20 graphene layers;
exposing the sheet of graphene-based material comprising multi-layer graphene to a particle beam having an ion energy of at least about 1500 eV to produce a plurality of damage tracks in the multi-layer graphene, the damage tracks extending entirely through the basal planes of the multiple graphene sheets; and
exposing the sheet of graphene-based material comprising multi-layer graphene to a chemical etchant to remove carbon atoms from the graphene at the damage tracks and open a plurality of pores extending through the multiple graphene sheets.

2. The method of claim 1, wherein the chemical etchant is an oxidant.

3. The method of claim 2, wherein the oxidant is selected from the group consisting of ozone, an aqueous solution of potassium permanganate, an aqueous solution of potassium permanganate and sulfuric acid, an aqueous solution of potassium permanganate and potassium hydroxide and a solution of hydrogen peroxide and sulfuric acid.

4. The method of claim 1, wherein the ion energy is greater than 1.5 keV and less than 100 keV.

5. The method of claim 1, wherein the ion energy is greater than 1.5 keV and less than 10 keV.

6. The method of claim 1, wherein the particle beam comprises ions selected from the group consisting of Xe+ ions, Ne+ ions and Ar+ ions.

7. The method of claim 1, wherein the particle beam comprises xenon ions.

8. The method of claim 1, wherein the particle beam comprises ions selected from the group consisting of tropyllium ions and ferrocenium ions.

9. The method of claim 1, wherein the graphene is disposed on a substrate when producing the damage tracks.

10. The method of claim 9, wherein the substrate is a metal growth substrate.

11. A sheet of graphene-based material comprising multi-layer graphene having from 10 to 20 graphene layers and comprising a plurality of pores extending therethrough.

12. The sheet of graphene-based material of claim 11, wherein the size of the pores is less than or equal to 50 nm.

13. The sheet of graphene-based material of claim 11, wherein the pores range from 0.2 nm to 50 nm in size.

14. The sheet of graphene-based material of claim 11, wherein the pores range from 0.3 nm to 50 nm in size.

15. The sheet of graphene-based material of claim 11, wherein the sheet of graphene-based material is prepared by
providing a sheet of graphene-based material comprising multi-layer graphene having between about 10 and about 20 graphene layers;
exposing the sheet of graphene-based material comprising multi-layer graphene to a particle beam having an ion energy of at least about 1500 eV to produce a plurality of damage tracks in the multi-layer graphene, the damage tracks extending entirely through the basal planes of the multiple graphene sheets; and
exposing the sheet of graphene-based material comprising multi-layer graphene to a chemical etchant to remove carbon atoms from the graphene at the damage tracks and open a plurality of pores extending through the multiple graphene sheets.

16. The sheet of graphene-based material of claim 11, wherein the sheet of graphene-based material is prepared by
providing a sheet of graphene-based material comprising multi-layer graphene having between about 10 and about 20 graphene layers;
exposing the sheet of graphene-based material comprising multi-layer graphene to a particle beam having an ion energy of at least about 1500 eV to produce a plurality of damage tracks in the multi-layer graphene, the damage tracks extending entirely through the basal planes of the multiple graphene sheets; and
exposing the sheet of graphene-based material comprising multi-layer graphene to a chemical etchant to remove carbon atoms from the graphene at the damage tracks and open a plurality of pores extending through the multiple graphene sheets,
wherein the graphene is disposed on a substrate when producing the damage tracks.