# Patent

## Title
Methods for perforating two-dimensional materials using a broad ion field

## Abstract

Perforating graphene and other two-dimensional materials with holes inclusively having a desired size range, a narrow size distribution, and a high hole density can be difficult to achieve. A layer in continuous contact with graphene, graphene-based materials and other two-dimensional materials can help promote hole formation. Processes for perforating a two-dimensional material can include exposing to an ion source a two-dimensional material in continuous contact with at least one layer, and interacting a plurality of ions from the ion source with the two-dimensional material and with the at least one layer. The ion source may be a broad ion beam.

## Background
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of priority under 35 U.S.C. §119 from U.S. Provisional Patent Applications 61/934,530, filed Jan. 31, 2014, which is incorporated herein by reference in its entirety.


STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT
Not applicable.
FIELD
The present disclosure generally relates to two-dimensional materials, and, more specifically, to processes for perforating two-dimensional materials.
BACKGROUND
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 planar lattice. In its various forms, graphene has garnered widespread interest for use in a number of applications, primarily due to its favorable combination of high electrical and thermal conductivity values, good in-plane mechanical strength, and unique optical and electronic properties. In many aspects, the properties of graphene parallel those of carbon nanotubes, since both nanomaterials are based upon an extended sp2-hybridized carbon framework. 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.
Because of its extended planar structure, graphene offers several features that are not shared with carbon nanotubes. Of particular interest to industry are large-area graphene films for applications such as, for example, special barrier layers, coatings, large area conductive elements (e.g., RF radiators or antennas), integrated circuits, transparent electrodes, solar cells, gas barriers, flexible electronics and the like. In addition, graphene films can be produced in bulk much more inexpensively at the present time than can carbon nanotubes.
Some envisioned applications for graphene and other two-dimensional materials are predicated upon forming a plurality of nanometer-scale holes in the planar structure of these nanomaterials. The process of forming holes in graphene and other two-dimensional materials will be referred to herein as “perforation,” and such nanomaterials will be referred to herein as being “perforated.” In a graphene sheet an interstitial aperture is formed by each six carbon atom ring structure in the sheet and this interstitial aperture is less than one nanometer across. In particular, this interstitial aperture is believed to be about 0.3 nanometers across its longest dimension (the center to center distance between carbon atoms being about 0.28 nm and the aperture being somewhat smaller than this distance). Perforation of sheets comprising two-dimensional network structures typically refers to formation of holes larger than the interstitial apertures in the network structure.
Perforation of graphene and other two-dimensional materials can modify the electrical properties of the material and its resistance to flow of fluid through the material. For example, the hole density of perforated graphene can be used to tune the electrical conductivity of this nanomaterial and in some instances can be used to adjust its band gap. Filtration applications are another area where perforated graphene and other perforated two-dimensional materials have generated considerable interest. Due to the atomic-level thinness of graphene and other two-dimensional materials, it can be possible to achieve high liquid throughput fluxes during filtration processes, even with holes being present that are only single-nanometer in size.
High performance, high selectivity filtration applications are dependent upon a sufficient number of holes of a desired size being present in a filtration membrane. Although a number of processes are known for perforating graphene and other two-dimensional materials, production of holes with a desired size range, a narrow size distribution, and a high hole density remains a challenge. At least one of these parameters is often lacking in conventional perforation processes.
Chemical techniques can be used to create holes in graphene and other two-dimensional materials. Exposure of graphene or another two-dimensional material to ozone or an atmospheric pressure plasma (e.g., an oxygen/argon or nitrogen/argon plasma) can effect perforation, but the holes are often lacking in terms of their density and size distribution. In many instances, it can be difficult to separately control hole nucleation and hole growth, so these processes often yield broad distributions of hole sizes. Further, many chemical perforation techniques produce holes that are at the extremes of 1) low hole density and small hole size, and 2) high hole density and large hole size. Neither of these extremes is particularly desirable for filtration applications. The first extreme is undesirable in terms of throughput flux, and the second extreme is undesirable for selectively excluding impurities that are smaller than the hole size.
Physical techniques can also be used to remove matter from the planar structure of two-dimensional materials in order to create holes. Hyperthermal ion beams tend to make pores in graphene and other two-dimensional materials that are too small for effective filtration to occur, primarily because the interaction of graphene and other two-dimensional materials with ions at hyperthermal velocities can be rather poor. The hyperthermal energy regime is defined as being intermediate between the thermal and low energy regimes. For example, a hyperthermal energy regime includes the energy range between 1 eV and 500 eV. Focused ion beams, in contrast, tend to make holes that are too few in number. Due to their very high energy flux, focused ion beams can also be exceedingly damaging to many substrates upon which the two-dimensional material is disposed. Because of their high energy requirements and small beam size, it is also not considered practical to utilize focused ion beams for perforating a large dimensional area.
Nanomaterials perforated with holes in a size range of about 0.3 nm to about 10 nm with a high hole density and narrow hole size distribution can be particularly difficult to prepare. Holes within this size range can be particularly effective for various filtration applications including, for example, reverse osmosis, molecular filtration, ultrafiltration and nanofiltration processes. As an example, holes in the size range 0.3 nm to 0.5 nm may be used for some gas separation processes. Holes in the size range 0.7 nm to 1.2 nm may be used for some desalination processes.
In view of the foregoing, scalable processes for perforating graphene and other two-dimensional materials in order to produce holes with a high hole density, narrow size distribution and a small hole size would be of considerable interest in the art. In particular, scalable processes to produce holes having a size, hole density, and size distribution suited for various filtration applications would be of considerable interest in the art. The present disclosure satisfies the foregoing needs and provides related advantages as well.
SUMMARY
In various embodiments, processes for perforating a two-dimensional material are described herein. In one aspect, exposure of a composite of a layer including the two-dimensional material and a layer of another material to a source of ions produces a plurality of holes in the two-dimensional material even when the energy and/or flux of the ions is relatively low. In an embodiment, the layer of the other material is not a layer or sheet of a two-dimensional material.
In some embodiments, the processes for perforation can include (1) exposing a two-dimensional material in contact with at least one layer of a material other than the two-dimensional material to an ion source and (2) interacting a plurality of ions from the ion source with the two-dimensional material and with the at least one layer. In an embodiment, the at least one layer is in continuous contact with the two-dimensional material while the two-dimensional material is being exposed to the ion source. In an embodiment, the ions introduce a plurality of defects in the two-dimensional material and an interaction of the ions with the at least one layer promotes expansion of the defects into a plurality of holes defined in the two-dimensional material. In embodiments, the ion source provides an ion energy ranging from 0.75 keV to 10 keV, from 1 keV to 10 keV, from 1 keV to 5 keV, from 2 keV to 10 keV, or from 5 keV to 10 keV. In embodiments, the ion source provides an ion dose 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 process comprises the steps of exposing a composite multilayered material to ions produced by an ion source, the multilayered material comprising a first layer comprising a two-dimensional first material and a second layer of a second material in contact with the first layer; and producing a plurality of holes in the two-dimensional first material by interacting a plurality of ions from the ion source, neutralized ions from the ion source or a combination thereof with the two-dimensional first material and with the second material. In an embodiment the ion source is a broad beam or flood source. As regards the neutralized ions, in some embodiments at least a portion of the ions originating from the ion source are neutralized as they interact with the multilayered material. For example, an ion may be neutralized either near the surface of a given layer or during collisions within the layer. In an embodiment, the first layer has a first side and a second side with the first side facing the ion source. The first side of the first layer may be termed the “frontside” of the first layer.
In an embodiment, the second layer is a “frontside layer” disposed on the first side of the first layer. During exposure of the multilayered material to the source of ions, at least a portion of the ions and/or neutralized ions interact with the material of the frontside layer, with a plurality of the ions and/or neutralized ions passing through the frontside layer before interacting with the layer comprising the two-dimensional material. In an embodiment, the frontside layer is removed after perforation. When the second layer is a “backside layer” disposed on the second side of the first layer, at least a portion of the ions and/or neutralized ions interact with the two-dimensional material of the first layer, with a plurality of ions and/or neutralized ions passing through the first layer before interacting with the backside layer. The multilayered material may further comprise a third layer of a third material. In an embodiment, the third layer is disposed on the opposite side of the first layer from the second layer, so that the first layer comprising the two-dimensional material contacts both frontside and backside layers of other materials.
In an embodiment, the second material is selected so that interaction of the ions and/or neutralized ions with the second material contributes to the perforation process. In an embodiment, the second material forms fragments upon interaction with the ions and/or neutralized ions. The type of fragments formed depends at least in part on the second material. The fragments may be atoms, ions or fragments of molecules (e.g. part of a polymer chain).
When the layer of the second material is a frontside layer, the thickness of the layer is thin enough to allow the ions and/or neutralized ions to penetrate to the layer comprising the two-dimensional material. In an embodiment, the average thickness of the layer of the second material is from 1 to 10 nm. Frontside layers may be continuous or discontinuous. In some embodiments, the at least one layer can be a layer such as, deposited silicon, a deposited polymer, a condensed gas or a condensed organic compound or any combination thereof. In embodiments, the polymer comprises the elements carbon and hydrogen and optionally further comprises one or more elements selected from the group consisting of silicon, oxygen, nitrogen, fluorine, chlorine and bromine. In embodiments, the polymer is a polycarbonate, a polyacrylate, a polyethylene oxide, an epoxide, a silicone, polytetrafluoroethylene (PTFE) or polyvinyl chloride (PVC). In an embodiment, the condensed gas is a noble gas such as xenon. In embodiments, the condensed organic compound is a mercaptan, an amine or an alcohol. In an embodiment, the organic compound comprises an alkyl group having 2 to 15, 2 to 10 or 5 to 15 carbon atoms.
When the layer of the second material is a backside layer, the layer may be thicker than the layer comprising the two-dimensional material. In an embodiment, the backside layer is 1 micrometer to 10 micrometers thick. In an additional embodiment the backside layer is 5 micrometers to 10 micrometers thick. In an embodiment, the layer provides a substrate for the layer of the two-dimensional material. In an embodiment, the backside layer is a growth substrate upon which the graphene or other two-dimensional material is grown. 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. In embodiments, the metal growth substrate is copper or nickel. In another embodiment, the backside layer can be a secondary substrate to which the graphene or other two-dimensional material has been transferred following growth.
In embodiments, the energy of the ions ranges from 0.01 keV to 10 keV, 0.5 keV to 10 keV, 0.75 keV to 10 keV, from 1 keV to 10 keV, from 1 keV to 5 keV, from 2 keV to 10 keV, or from 5 keV to 10 keV. In embodiments, ion energies greater than 0.75 keV or 1 keV are preferred when the two-dimensional material comprises a sheet of graphene-based material and further comprises at least some non-graphenic carbon-based material. 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 various embodiments, the two-dimensional material comprises a sheet of a graphene-based material. In an embodiment, the first layer comprises a sheet of a graphene-based material. In an embodiment, the 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. In an embodiment, the layer comprising the sheet of graphene-based material further comprises non-graphenic carbon-based material located on the surface of the sheet of graphene-based material. In an embodiment, the amount of non-graphenic carbon-based material is less than the amount of graphene. In embodiments, the amount of graphene in the graphene-based material is from 60% to 95% or from 75% to 100%.
In embodiments, the characteristic size of the perforation is from 0.3 to 10 nm, from 0.3 to 0.5 nm, from 0.4 to 10 nm, from 0.5 to 2.5 nm, from 0.5 to 10 nm, from 5 nm to 20 nm, from 0.7 nm to 1.2 nm, from 10 nm to 50 nm, from 50 nm to 100 nm from 50 nm to 150 nm, or from 100 nm to 200 nm. In an embodiment, the average pore size is within the specified range. In embodiments, 70% to 99%, 80% to 99%, 85% to 99% or 90 to 99% of the perforations fall within a specified range, but other pores fall outside the specified range. If the pores falling outside the specified range are larger than specified in the range, these pores may be termed “non-selective.”
In more specific embodiments, the processes can include providing a sheet of a graphene-based material on a metal growth substrate, exposing the sheet of a graphene-based material to an ion source providing an ion dose 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 and having an ion energy ranging from 0.75 keV to 10 keV, from 1 keV to 10 keV, from 1 keV to 5 keV, from 2 keV to 10 keV, or from 5 keV to 10 keV, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the metal growth substrate, in which the ions introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the metal growth substrate ejects toward the graphene a plurality of layer fragment from the metal growth substrate, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. The metal growth substrate is disposed on a side of the graphene opposite the ion source and constitutes a backside layer. In an embodiment when the layer is a metal growth substrate, the layer fragments constitute metal atoms or metal ions.
In other more specific embodiments, the processes includes exposing a sheet of a graphene-based material having thereon a frontside layer to an ion source providing an ion dose 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 and having an ion energy ranging from 0.75 keV to 10 keV, from 1 keV to 10 keV, from 1 keV to 5 keV, from 2 keV to 10 keV, or from 5 keV to 10 keV, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the frontside layer to introduce a plurality of defects in the graphene. In an embodiment, interaction of the ions and/or neutralized ions with the frontside layer ejects toward the graphene a plurality of layer fragments, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. The frontside layer is disposed on the same side of the graphene as the ion source.
In still other more specific embodiments, the processes can include exposing a sheet of a graphene-based material present on a backside layer to an ion source providing an ion dose 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 and having an ion energy ranging from 0.75 keV to 10 keV, from 1 keV to 10 keV, from 1 keV to 5 keV, from 2 keV to 10 keV, or from 5 keV to 10 keV, and interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the backside layer to introduce a plurality of defects in the graphene. The backside layer is located on a side of the graphene opposite the ion source. In an embodiment, the backside layer disperses an impact energy of the ions and/or neutralized ions with the backside layer into an area of the graphene surrounding the defects created upon interacting the ions and/or neutralized ions with the graphene and promotes expansion of the defects into holes.
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 description below taken in conjunction with the drawings.



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 and FIG. 2 show illustrative schematics of a frontside layer in continuous contact with graphene or another two-dimensional material;
FIG. 3A, FIG. 3B and FIG. 3C show illustrative schematics demonstrating how the interaction of an ion with a frontside layer and with graphene or another two-dimensional material can define a hole in the graphene or other two-dimensional material; and
FIG. 4A, FIG. 4B and FIG. 4C show illustrative schematics demonstrating how the interaction of an ion with a backside layer and with graphene or another two-dimensional material can define a hole in the graphene or other two-dimensional material.



DETAILED DESCRIPTION
The present disclosure is directed, in part, to various processes for producing a plurality of holes in graphene, graphene-based materials and other two-dimensional materials. In an embodiment, the first layer comprises a sheet of graphene-based material. 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 an embodiment, graphene-based materials also include materials which have been formed by stacking single or multilayer graphene sheets. In embodiments, multilayer graphene includes 2 to 20 layers, 2 to 10 layers or 2 to 5 layers. In embodiments, graphene is the dominant material in a graphene-based material. For example, a graphene-based material comprises at least 30% graphene, or at least 40% graphene, or at least 50% graphene, or at least 60% graphene, or at least 70% graphene, or at least 80% graphene, or at least 90% graphene, or at least 95% 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%.
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. “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 comprises a sheet of single or multilayer graphene or a combination thereof. In an embodiment, the sheet of graphene-based material is a sheet of single or multilayer graphene or a combination thereof. In another embodiment, the sheet of graphene-based material is a sheet comprising a plurality of interconnected single or 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 0.34 to 10 nm, from 0.34 to 5 nm, or from 0.34 to 3 nm. 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.
In an embodiment, the layer comprising the sheet of graphene-based material further comprises non-graphenic carbon-based material located on the surface of the sheet of graphene-based material. 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. Non-carbon elements which may be incorporated in the non-graphenic carbon include, but are not limited to, hydrogen, oxygen, silicon, copper and iron. In embodiments, 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%.
Such 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 present disclosure is also directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of holes ranging from about 0.3 nm to about 10 nm in size. The present disclosure is further directed, in part, to perforated graphene, perforated graphene-based materials and other perforated two-dimensional materials containing a plurality of holes ranging from about 0.3 nm to about 10 nm in size and having a narrow size distribution, including but not limited to a 1-10% deviation in size or a 1-20% deviation in size. In an embodiment, the characteristic dimension of the holes is from 0.5 nm to 10 nm. 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
As discussed above, conventional processes for perforating graphene and other two-dimensional materials with a plurality of holes can be limited in terms of the obtained hole density, hole size and size distribution. Perforated nanomaterials having small holes with an effective size of about 10 nm or less can be particularly difficult to produce with a sufficient hole density and size distribution to support many intended applications. Filtration applications, for example, can be significantly impacted by an inability to produce holes of a selective size and hole density, as selectivity and throughput flux can be severely impacted. Moreover, presently available techniques for perforating graphene and other two-dimensional materials are not believed to be scalable to large dimensional areas (e.g., one to tens of square centimeters or more) in order to support commercial production efforts.
Current methods for perforating graphene and other two-dimensional materials include both chemical and physical processes. Chemical processes generally involve both hole nucleation and hole growth stages. However, hole nucleation and hole growth are usually difficult to separate from one another, thereby leading to a broad distribution of hole sizes. Physical processes generally involve a brute force knockout of atoms from the planar structure of the two-dimensional material. However, physical processes are rather energy inefficient, especially when considering their scaleup for commercial production efforts. Moreover, high energy ions can actually interact rather poorly with graphene and other two-dimensional materials, leading to a poor yield of atoms ejected during the knockout process.
In an embodiment, energetic ion perforation processes for graphene, graphene-based materials and other two-dimensional materials can be significantly enhanced by conducting the perforation process with at least one layer of a second material in continuous contact with the graphene or other two-dimensional material during its exposure to a broad field or flood ion source. A broad field or flood ion source can provide an ion flux which is significantly reduced compared to a focused ion beam. In an embodiment, the ion flux is from 0.1 nA/mm2 to 100 nA/mm2. By utilizing a broad ion field in conjunction with at least one layer in continuous contact with the graphene or other two-dimensional material, significantly improved perforation can be obtained in the form of small hole sizes, narrow size distributions, and high hole densities. In an embodiment, the hole density is characterized by the spacing between the holes. In an embodiment where the average pore size is from 0.5 nm to 2.5 nm, the average spacing between the pores is from 0.5 nm to 5 nm. The processes of the present disclosure are readily distinguished from focused ion beam processes, which have higher ion fluxes and/or ion energies. The broad ion field processes of the present disclosure are considerably more scalable in terms of areal coverage for commercial processing. Depending on their location, the layer(s) in continuous contact with the graphene or other two-dimensional material can impact the perforation process in several different ways, as discussed hereinafter.
In embodiments, the energetic ion perforation processes described herein utilize the knockout approach of physical perforation processes while also facilitating a discrete hole growth stage, like chemical processes. Unlike conventional chemical and physical perforation processes, however, the perforation processes of the present disclosure advantageously separate the hole nucleation and growth stages from one another while still allowing nucleation and growth to occur in a highly concerted fashion. In embodiments, the one or more layers in continuous contact with the graphene or other two-dimensional material allow highly concerted nucleation and growth to occur. Specifically, the one or more layers allow hole nucleation to be followed in short order by hole growth as a result of a single incident ion impact with the graphene or other two-dimensional material In conventional processes, hole nucleation and growth are not concerted. Because the hole nucleation and growth are separated but concerted stages in the processes of the present disclosure, a narrow hole size distribution can be obtained. Moreover, the processes of the present disclosure are advantageously suited to produce holes that are about 10 nm in size or under, which can be desirable for a number of applications, including filtration. Further, the hole size and/or hole density can be adjusted to suit the needs of a particular application. In an embodiment, a higher fluence or exposure time increases the number of holes (until the holes begin to overlap). Higher ion energies can either increase or decrease the hole size depending on the details of the interaction. The hole density can be modulated by adjusting the exposure time of the graphene or other two-dimensional material to the ion source.
Thus, the processes of the present disclosure are capable of providing all three of the key needs for perforated graphene, graphene-based materials and other two-dimensional materials (small hole size, narrow size distribution, and high hole density). Moreover, because they make use of a broad ion field for affecting perforation, the processes of the present disclosure are advantageously scalable to large dimensional areas and can support commercial processing efforts.
As indicated above, the broad ion field used to affect perforation in embodiments of the processes of the present disclosure provides ions with an ion energy ranging between about 0.75 keV and about 10 keV. In an embodiment the ion energy ranges from 1 keV to 10 keV. In an additional embodiment the ion energy ranges from 1 keV to 5 keV. In a further embodiment the ion energy ranges from 2 keV to 10 keV. In an additional embodiment the ion energy ranges from 5 keV to 10 keV. Some ions having energies within this range may interact poorly with graphene and other two-dimensional materials, producing only point defects in the planar structure in the form of 1-2 knocked out atoms per incident ion (single-vacancies and di-vacancies). In an embodiment, the holes produced by the processes of the present disclosure produce holes larger in size than such a point defect. The processes of the present disclosure, specifically the layer(s) in continuous contact with the graphene or other two-dimensional material, can produce holes larger in size than would be predicted on the basis of the ion energy alone. Without wishing to be bound by any particular belief, contact of the frontside or backside layer with the two-dimensional material during ion irradiation is believed to advantageously promote expansion of the defects into holes of meaningful size through converting the high energy incident ions into a thermal bombardment of the graphene or other two-dimensional material. Layers in different locations with respect to the ion source can facilitate this effect in several ways through bond energy mismatch, as discussed further herein below.
Although certain embodiments are described herein with graphene as the two-dimensional material, it is to be recognized that other two-dimensional materials can be used similarly in alternative embodiments unless otherwise specified herein. Thus, considerable flexibility can be realized by practicing the disclosure in order to produce a particular perforated two-dimensional material having a desired set of properties.
In various embodiments, processes described herein can include exposing a two-dimensional material in continuous contact with at least one layer to an ion source, and interacting a plurality of ions and/or neutralized ions from the ion source with the two-dimensional material and with the at least one layer. In embodiments, the ions and/or neutralized ions introduce a plurality of defects in the two-dimensional material and an interaction of the ions and/or neutralized ions with the at least one layer promotes expansion of the defects into a plurality of holes defined in the two-dimensional material. The at least one layer is in continuous contact with the two-dimensional material while the two-dimensional material is being exposed to the ion source.
In various embodiments, the two-dimensional material comprises graphene, molybdenum sulfide, or boron nitride. In more particular embodiments, the two-dimensional material can be graphene. Graphene according to the embodiments of the present disclosure can include single-layer graphene, multi-layer graphene, or any combination thereof. Other nanomaterials having an extended two-dimensional molecular structure can also constitute the two-dimensional material in the various embodiments of the present disclosure. 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 embodiments of the present disclosure. Choice of a suitable two-dimensional material for a particular application can be determined by a number of factors, including the chemical and physical environment into which the graphene or other two-dimensional material is to be terminally deployed.
In various embodiments of the present disclosure, the holes produced in the graphene or other two-dimensional material can range from about 0.3 nm to about 10 nm in size. In a more specific embodiment, the holes can range from about 0.5 nm to about 2.5 nm in size. In an additional embodiment, the hole size is from 0.3 to 0.5 nm. In a further embodiment, the hole size is from 0.5 to 10 nm. In an additional embodiment, the hole size is from 5 nm to 20 nm. In a further embodiment, the hole size is from 0.7 nm to 1.2 nm. In an additional embodiment, the hole size is from 10 nm to 50 nm. In embodiments where larger hole sizes are preferred, the hole size is from 50 nm to 100 nm, from 50 nm to 150 nm, or from 100 nm to 200 nm. Holes within these size ranges can be particularly desirable for filtration applications. The 0.5 nm to 2.5 nm size range can be particularly effective for use in reverse osmosis filtration applications.
Contact times for the graphene or other two-dimensional material with the ion source can range between about 0.1 seconds and about 120 second in order to produce an ion fluence sufficient to produce these hole densities. Longer contact times can be used if desired in order to modulate the number of holes obtained in the planar structure.
The ion source inducing perforation of the graphene or other two-dimensional material in the embodiments of the present disclosure is considered to provide a broad ion field, also commonly referred to as 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 an embodiment, the environment also contains background amounts (e.g. on the order of 10−5 torr) of oxygen (O2), nitrogen (N2) or carbon dioxide (CO2). As indicated above, in an embodiment the ion source provides an ion dose ranging from 1×1010 ions/cm2 to 1×1017 ions/cm2 and having an ion energy ranging from 0.75 keV to 10 keV. In more particular embodiments, the ion energy can range from 1 keV to 10 keV or from 5 keV to 10 keV. In some embodiments, the ion dose can range between about 1×1011 ions/cm2 and about 1×1015 ions/cm2, between about 1×1012 ions/cm2 and about 1×1014 ions/cm2, or from 1×1013 ions/cm2 to 1×1019 ions/cm2. In an embodiment, the ion dose ranges from 1×1010 ions/cm2 to 1×1017 ions/cm2. In an additional embodiment the ion does ranges from 1×1011 ions/cm2 to 1×1015 ions/cm2. In a further embodiment, the ion dose ranges from 1×1013 ions/cm2 to 1×1019 ions/cm2. In an embodiment, the flux or beam current density is from 10 nA/nm2 to 100 nA/nm2. In embodiments, the ion beam may be perpendicular to the surface of the layers of the multilayered material (incidence angle of 0 degrees) or the incidence angle may be from 0 to 45 degrees, 0 to 20 degrees, 0 to 15 degrees or 0 to 10 degrees.
The ion source can provide any of a variety of ions suitable for inducing perforations in graphene, graphene-based materials and other two-dimensional materials. In an embodiment, the ion is singly charged. In another embodiment, the ion is multiply charged. In an embodiment, the ion is a noble gas ion (ion of an element from Group 18 of the periodic table). In an embodiment, the ion is other than a helium ion. In an embodiment the ion is an organic ion or organometallic ion. 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. In illustrative embodiments, ions that can be supplied from the ion source to induce perforation of graphene or another two-dimensional material can include Xe+ ions, Ne+ ions, Ar+ ions, tropyllium ions (C7H7+) and ferrocenium ions [(C5H5)2Fe+]. In embodiments, when the ions are Xe+ ions, Ne+ ions, Ar+ ions, the dose is 1×1011 ions/cm2 to 1×1015 ions/cm2. In embodiments, when the ion comprises a plurality of elements (such as tropyllium and ferrocenium), the fluence is 1×1011 ions/cm2 to 1×1015 ions/cm2. In an embodiment, helium ions are provided with a dose from 1×1013 ions/cm2 to 1×1019 ions/cm2. The chosen ion and its energy can determine, at least in part, the size of the holes obtained in the graphene or other two dimensional material. In particular embodiments, the chosen ion and its energy can be chosen to eject fragments from the at least one layer toward the graphene or other two-dimensional material.
In an embodiment, the temperature of the multilayer composite is controlled during ion bombardment. In embodiment, the temperature is controlled from −130° C. to 200° C. or from −130° C. to 100° C. In an embodiment, the temperature may be selected to allow condensation of a gas on the frontside of the two-dimensional material. In an embodiment, where a metal backside layer is present, the temperature may be controlled from 50° C. to 80° C. The one or more layers in continuous contact with the graphene or other two-dimensional material can be a frontside layer or a backside layer, or both can be present. The term “frontside” refers to the condition of being on the same side of the two-dimensional material as the ion source. The term “backside” refers to the condition of being on the side of the two-dimensional material opposite the ion source. Depending on its location, the at least one layer can be natively or exogenously present on the graphene or other two-dimensional material, or the at least one layer can be intentionally deposited after formation of the graphene or other two dimensional material. For example, a metal growth substrate can constitute a backside layer in various embodiments of the present disclosure.
Generally, the at least one layer has a bond energy that is weaker than that of graphene or the two-dimensional material, which is characterized by strong bonds. That is, when the at least one layer is interacted with the ion source, bonds are broken in the at least one layer in preference to the graphene or other two-dimensional material due to a bond energy mismatch. In some embodiments, the at least one layer can be a deposited layer such as deposited silicon, a deposited polymer, or any combination thereof. If the graphene or other two-dimensional material remains on its metal growth substrate, a deposited layer can constitute a frontside layer. However, if the graphene or other two-dimensional material has been removed from its metal growth substrate, a deposited layer can constitute either a frontside layer or a backside layer. Deposited polymers that can include any polymer material that suitably adheres to the graphene-based material or other two-dimensional material such as silicone polymers, for example. In an embodiment, the deposited polymer does not completely delaminate from the graphene-based material during ion bombardment. Other suitable polymer layers can be envisioned by one having ordinary skill in the art.
In some embodiments, a frontside layer deposited on the graphene or other two-dimensional material can have a thickness ranging between about 1 nm and about 10 nm. Thicker frontside layers can also be present, if desired. Although the frontside layer can be deposited exogenously during synthesis of the graphene or other two-dimensional material, the frontside layer can also be deposited in a separate operation in other embodiments. For example, the frontside layer can be deposited by sputtering, spraying, spin coating, atomic layer deposition, molecular beam epitaxy or like techniques in some embodiments.
Various layers will now be further described according to their location and function.
In some embodiments, the at least one layer can be at least a frontside layer disposed on the same side of the two-dimensional material as the ion source. Illustrative frontside layers can include those described above. When a frontside layer is present, ions from the ion source interact with the frontside layer before interacting with the graphene or other two-dimensional material. As discussed hereinafter, this type of interaction can still promote the creation and expansion of holes in the planar structure of the graphene or other two-dimensional material by ejecting layer fragments from the frontside layer and impacting the layer fragments with the graphene or other two-dimensional material to form holes therein. Since the frontside layer is relatively thin, it has a low stopping power and allows the ions and/or neutralized ions to penetrate through the frontside layer to further interact with the graphene.
In an embodiment, ion bombardment of the frontside layer generates a plume of more, but lower energy particles, impinging on the graphene or other two dimensional material. In more specific embodiments, processes of the present disclosure can include ejecting toward the two-dimensional material a plurality of layer fragments from the frontside layer upon interaction of ions and/or neutralized ions therewith, and impacting the layer fragments with the two-dimensional material in an area of the two-dimensional material surrounding the defects created upon interacting the ions and/or neutralized ions with the two-dimensional material and promoting expansion of the defects into holes. Layer fragments can include atoms, ions, molecules or molecular fragments displaced from the frontside layer upon interaction of a high energy ion with the frontside layer. A frontside layer can be present in combination with a backside layer or a frontside layer can be present alone. Functions of the backside layer are discussed further below.
Without being bound by theory or mechanism, it is believed that hole definition or generation in the presence of a frontside layer can take place due to several synergistic effects. First, the graphene or other two-dimensional material can have an enhanced degree of chemical reactivity in the vicinity of the defects initially created by the high energy ions and/or neutralized ions. Second, the layer fragments from the frontside layer can turn a single impact event at the frontside layer into a plurality of impact events at the graphene or other two-dimensional material. Third, the layer fragments have a lower energy than do the incident high energy ions, thereby increasing the likelihood of successfully interacting with the graphene or other two-dimensional material in order to define a hole. Finally, because the frontside layer and the graphene or other two-dimensional material are in continuous contact with one another, the geometric spread of the layer fragments during their transit to the graphene or other two-dimensional material is minimal, thereby limiting the hole size. Thus, the combination of enhanced chemical reactivity in the vicinity of the defects and the more efficient interaction of the layer fragments with the graphene or other two-dimensional material can result in the definition of a hole.
FIGS. 1 and 2 show illustrative schematics of frontside layer 2 in continuous contact with graphene 4 or another two-dimensional material. In FIG. 1, only frontside layer 2 is present, and in FIG. 2, both frontside layer 2 and backside layer 6 are present. Ion source 8 is configured to supply a dose of ions 10 for perforating graphene 4.
FIGS. 3A, 3B and 3C show illustrative schematics demonstrating how the interaction of an ion with a frontside layer and with graphene or another two-dimensional material can define a hole in the graphene or other two-dimensional material. In the interest of clarity of description and depiction, frontside layer 2 and graphene 4 are shown in an exploded view and in a spaced apart configuration in FIGS. 3A and 3B, rather than in their true configuration of being in continuous contact with one another. FIG. 3A shows frontside layer 2 and graphene 4 after ion 10 has impacted and passed through the frontside layer. Layer fragments 12 are ejected from frontside layer 2 and are scattered at thermal velocities/energies and/or hyperthermal velocities/energies toward graphene 4. In an embodiment this scattering may be referred to as ballistic scattering. A defect 13 is created in the frontside layer. A defect 14 (not shown in FIG. 3A) may be introduced in graphene 4 upon the passage of ion 10 through the planar structure of graphene 4. Again, it is to be emphasized that frontside layer 2 and graphene 4 are, in fact, in continuous contact with one another, thereby minimizing the degree of ballistic scattering that takes place as layer fragments 12 transit from frontside layer 2 to graphene 4. In an embodiment, layer fragments 12 impact graphene 4 in close proximity to defect 14, where the chemical reactivity is enhanced. In an embodiment, layer fragments 12 then result in expansion of defect 14 to define hole 16, as shown in FIG. 3B. FIG. 3C shows frontside layer 2 and graphene 4 in their true continuous contact configuration after the creation of hole 16. As exemplified by FIGS. 3A-3C, the stages of hole nucleation (i.e., formation of a defect in the graphene by direct interaction of the ion) and hole growth (i.e., impact of layer fragments 12 with graphene4) are separated, yet highly concerted processes. Therefore, holes 16 of defined size and having a narrow size distribution can be obtained.
As shown in FIG. 3B, frontside layer 2 can at least partially cover hole 16 following its creation. In some embodiments, frontside layer 2 can be removed following the definition of holes 16 in order to increase the effective permeability of graphene 4. Illustrative frontside layer removal techniques can include, for example, oxidation, solvent washes, heating, or any combination thereof. Oxidation techniques include, but are not limited to, ultraviolet-oxygen (UVO) treatment using reactive oxygen species. Depending on the composition of frontside layer 2, one having ordinary skill in the art will be able to choose a suitable removal process.
In some embodiments, the at least one layer in continuous contact with the graphene or other two dimensional material can be a backside layer disposed on a side of the graphene or other two-dimensional material opposite the ion source. In an embodiment, the backside layer is a metal growth substrate upon which the graphene or other two-dimensional material is grown, or the backside layer can be a secondary substrate to which the graphene or other two-dimensional material has been transferred following growth. In an embodiment, the secondary substrate is polymeric, including porous polymeric membranes. In either case, the backside layer can have a thickness that is significantly greater than that of the graphene or other two-dimensional material. Accordingly, the backside layer can have a much higher stopping power for the energetic ions and/or neutralized ions than does the graphene or other two-dimensional material. Upon stopping the energetic ions, the backside layer can disperse an impact energy of the ions and/or neutralized ions with the backside layer into an area of the graphene or other two-dimensional material surrounding the defects created upon interacting the ions with the two-dimensional material and promoting the expansion of the defects into holes. In more specific embodiments, a backside layer promotes expansion of defects in a two-dimensional material into holes in a manner somewhat similar to that described above for a frontside layer, in which fragments are directed towards the two-dimensional material. The backside layer may also promote formation of defects in the two-dimensional material. For example, even when an ion or neutralized ion does not form a hole when passing through the two-dimensional material, impact of the ions and/or neutralized ions with the backside layer may cause a small region in the backside layer to rapidly heat and expand, opening a hole in the graphene or other two-dimensional material.
FIGS. 4A, 4B and 4C show illustrative schematics demonstrating how the interaction of an ion with a backside layer and with graphene or another two-dimensional material can define a hole in the graphene or other two-dimensional material. Again, in the interest of clarity of description and depiction, backside layer 6 and graphene 4 are shown in an exploded view and in a spaced apart configuration in FIGS. 4A and 4B, rather than in their true configuration of being in continuous contact with one another. FIG. 4A shows graphene 4 or another two-dimensional material and backside layer 6 immediately after an ion has passed through graphene 4 and impacted backside layer 6. Defect 14 is generated in graphene 4 upon passage of the ion therethrough. In the case of backside layer 6, the ion embeds in impact region 20, thereby resulting in ejection of layer fragments 12′ therefrom. In FIG. 4A, impact region 20 is shown as a crater. Layer fragments 12′ can include those described above for frontside layer 2. For example, when backside layer 6 is the metal growth substrate upon which graphene 4 or another two-dimensional material is grown, layer fragments 12′ can be metal atoms or metal ions sputtered from the metal growth substrate upon kinetic energy transfer from the ion to backside layer 6. Layer fragments 12′ are ejected toward graphene 4 at thermal velocities and again impact in close proximity to defect 14 to result in its expansion into hole 16, as depicted in FIG. 4B. In the configuration of FIGS. 4A and 4B, layer fragments 12′ impact graphene 4 from its underside, rather than from its topside as in FIGS. 3A and 3B. Again, it is to be emphasized that backside layer 6 and graphene 4 are, in fact, in continuous contact with one another, thereby minimizing the degree of scattering that takes place as layer fragments 12′ transit from backside layer 6 to graphene 4. As shown, layer fragments 12′ impact graphene 4 in close proximity to defect 14 to where the chemical reactivity is enhanced. FIG. 4C shows backside layer 6 and graphene 4 in their true continuous contact configuration after the creation of hole 16. As exemplified by FIGS. 4A-4C, the stages of hole nucleation (i.e., formation of defect 14) and hole growth (i.e., impact of layer fragments 12′ with graphene 4) are again separated, yet highly concerted processes. Because there is minimal geometric scattering as layer fragments 12′ transit between backside layer 6 and graphene 4, holes 16 having a defined size and a narrow size distribution can be obtained.
Illustrative metal growth substrates upon which graphene, graphene-based materials and other two-dimensional materials can be grown and which can serve as the backside layer in the embodiments of the present disclosure include various metal surfaces containing a transition metal. In the case of graphene, for example, copper or nickel can be particularly effective for promoting epitaxial graphene growth. In some embodiments, the metal growth substrate can be formed substantially entirely of a metal, such as a metal foil or a metal sheet. In other embodiments, the metal growth substrate can include a metal surface on a different subsurface material. For example, a ceramic substrate having a metal surface can be used as the metal growth substrate and backside layer in various embodiments of the present disclosure.
Accordingly, in some embodiments, processes of the present disclosure can include ejecting toward the two-dimensional material, such as graphene, a plurality of layer fragments from the backside layer upon interaction of the ions and/or neutralized ions therewith, and impacting the layer fragments with the two-dimensional material in an area of the two-dimensional material surrounding the defects and promoting expansion of the defects into holes. That is, the backside layer can promote energy transfer to the graphene or other two-dimensional material in the form of layer fragments having thermal velocities in order to promote the creation of holes in the graphene or other two-dimensional material.
In some embodiments, both a frontside layer and a backside layer can be in continuous contact with the graphene or other two-dimensional material as it is interacted with the ions and/or neutralized ions from the ion source. The layer fragments generated from both the frontside layer and the backside layer can work in concert with one another to expand the generated defects in the graphene or other two-dimensional material into a plurality of holes. For example, in some embodiments, layer fragments generated from a suitable frontside layer and metal atoms or metal ions generated from a backside metal growth substrate can impact graphene from both sides of its planar structure to promote the creation of holes therein. This can be particularly effective for perforating multi-layer two-dimensional materials, such as multi-layer graphene, for example by holding the particles in a local region.
Accordingly, in embodiments where both a frontside layer and a backside layer are present, processes of the present disclosure can include ejecting toward the graphene or other two-dimensional material a plurality of layer fragments from the frontside layer upon interaction of the ions and/or neutralized ions therewith, ejecting toward the graphene or other two-dimensional material a plurality of layer fragments from the backside layer upon interaction of the ions and/or neutralized ions therewith, and impacting the layer fragments from both layers with the graphene or other two-dimensional material in an area surrounding the defects created upon interacting the ions and/or neutralized ions with the graphene or other two-dimensional material and promoting the expansion of the defects into holes.
In particular embodiments, processes of the present disclosure can include providing graphene on a metal growth substrate, exposing the graphene to an ion source, interacting a plurality of ions from the ion source with the graphene and with the metal growth substrate to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the metal growth substrate ejecting toward the graphene a plurality of layer fragments including metal ions or metal atoms from the metal growth substrate, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1011 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV. The metal growth substrate is disposed on a side of the graphene opposite the ion source and constitutes a backside layer.
In some embodiments, the graphene can be coated with a frontside layer opposite the metal growth substrate that is disposed on the same side of the graphene as the ion source (see FIG. 2, for example). The frontside layer can be formed from various materials and can have a thickness ranging between about 1 nm and about 10 nm, for example. In some embodiments, the processes can further include removing the frontside layer after defining the plurality of holes in the graphene.
In other particular embodiments, processes of the present disclosure can include exposing graphene to an ion source, the graphene having thereon a frontside layer disposed on the same side of the graphene as the ion source, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the frontside layer to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the frontside layer ejecting toward the graphene a plurality of layer fragments, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1011 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV.
In still other particular embodiments, processes of the present disclosure can include exposing graphene to an ion source, the graphene being present on a backside layer located on a side of the graphene opposite the ion source, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the backside layer to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the backside layer dispersing an impact energy of the ions and/or neutralized ions with the backside layer into an area of the graphene surrounding the defects created upon interacting the ions with the graphene an promoting expansion of the defects into holes. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1010 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV.
In more specific particular embodiments, processes of the present disclosure can include exposing graphene to an ion source, the graphene being present on a backside layer located on a side of the graphene opposite the ion source, interacting a plurality of ions and/or neutralized ions from the ion source with the graphene and with the backside layer to introduce a plurality of defects in the graphene and an interaction of the ions and/or neutralized ions with the backside layer ejecting toward the graphene a plurality of layer fragments, and expanding the defects in the graphene with the layer fragments to define a plurality of holes in the graphene. In an embodiment, the ion source provides to the graphene an ion dose ranging between about 1×1010 ions/cm2 and about 1×1017 ions/cm2 and having an ion energy ranging between about 0.75 keV and about 10 keV.
The perforated graphene, graphene-based materials and other two-dimensional materials described herein can be used in a variety of applications including filtration, electronics, barrier layers and films, gas barriers, and the like. Illustrative filtration applications in which the perforated graphene, graphene-based materials and other perforated two-dimensional materials can be used include, for example, reverse osmosis, molecular filtration, ultrafiltration and nanofiltration processes. When used in various filtration processes, the perforated graphene or other perforated two-dimensional material can be perforated and then transferred to a porous secondary substrate, where the perforated graphene or other perforated two-dimensional filtration serves as the active filtration membrane.
Although the invention has been described with reference to the disclosed embodiments, those skilled in the art will readily appreciate that these only illustrative of the invention. It should be understood that various modifications can be made without departing from the spirit of the invention. The invention 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 invention. Additionally, while various embodiments of the invention have been described, it is to be understood that aspects of the invention may include only some of the described embodiments. Accordingly, the invention 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 claim.

## Claims

1. A process comprising:
exposing a multilayered material to ions provided by an ion source, the multilayered material comprising a first layer comprising a two-dimensional first material and a second layer of a second material in contact with the first layer, the ions being provided with an ion energy ranging from 1.0 keV to 10 keV, and a flux from 0.1 nA/mm2 to 100 nA/mm2; and
producing a plurality of holes in the two-dimensional first material by interacting a plurality of ions provided by the ion source, neutralized ions or a combination thereof with the two-dimensional first material and with the second material.

2. The process of claim 1, wherein the ion energy is from 1 keV to 5 keV.

3. The process of claim 1, wherein the ion source is a broad beam source.

4. The process of claim 1, wherein the multilayered material is exposed to an ion dose ranging from 1×1011 ions/cm2 to 1×1015 ions/cm2 and the ion source provides ions selected from the group consisting of Xe+ ions, Ne+ ions, or Ar+ ions.

5. The process of claim 1, wherein the multilayered material is exposed to an ion dose ranging from 1×1011 ions/cm2 to 1×1015 ions/cm2 and the ion source provides organic or organometallic ions having a molecular mass from 90 to 200.

6. The process of claim 5, wherein the ion is selected from the group consisting of tropyllium ions and ferrocenium ions.

7. The process of claim 1, wherein the two-dimensional first material comprises graphene.

8. The process of claim 7, wherein the first layer comprises a sheet of a graphene-based material.

9. The process of claim 1, wherein the characteristic dimension of the holes is from 0.5 nm to 2.5 nm.

10. The process of claim 1, wherein the characteristic dimension of the holes is from 1 nm to 10 nm.

11. The process of claim 1, wherein the first layer has a first side and a second side, the first side facing the ion source and the second layer being disposed on the second side of the first layer and having a thickness greater than that of the first layer.

12. The process of claim 11, wherein the second material comprises a metal.

13. The process of claim 12, wherein the second layer comprises a metal growth substrate for the two-dimensional first material and the fragments comprise metal atoms or metal ions ejected from the metal growth substrate.

14. The process of claim 11, wherein the interaction of at least a portion of the ions, neutralized ions, or a combination thereof with the first material introduces a plurality of defects in the first material, a plurality of the ions, neutralized ions, or a combination thereof pass through the first layer comprising the first material to interact with the second material and interaction of the ions, neutralized ions, or a combination thereof with the second material of the second layer promotes expansion of the defects into holes.

15. The process of claim 14, wherein the second material interacts with the ions, neutralized ions, or a combination thereof to produce fragments of the second material, at least some of the fragments of the second material being directed towards the two dimensional material.

16. The process of claim 11, wherein the multilayered material further comprises a third layer of a third material disposed on the first side of the first layer, the third layer having an average thickness ranging from 1 nm to 10 nm.

17. The process of claim 16, wherein the third layer comprises comprises deposited silicon, a deposited polymer, a condensed gas, a condensed organic compound or a combination thereof.

18. The process of claim 16, wherein a plurality of the ions, neutralized ions, or a combination thereof pass through the third layer of the third material to interact with the first material, the interaction of ions, neutralized ions, or a combination thereof with the first (2D) material introducing a plurality of defects in the first material, a plurality of the ions, neutralized ions, or a combination thereof pass through the first layer comprising the first material to interact with the second material and the interaction of at least a portion of the ions, neutralized ions, or a combination thereof with the second material and the third material promotes expansion of the defects into holes.

19. The process of claim 18, wherein the third material interacts with ions, neutralized ions, or a combination thereof to produce fragments of the third material, at least some of the fragments of the third material being directed towards the two dimensional material.

20. The process of claim 1, wherein the first layer has a first side and a second side, the first side facing the ion source and the second layer being disposed on the first side of the first layer, the second layer having an average thickness ranging from 1 nm to 10 nm.

21. The process of claim 20, wherein the second layer comprises comprises deposited silicon, a deposited polymer, a condensed gas, a condensed organic compound or a combination thereof.

22. The process of claim 20, wherein a plurality of the ions, neutralized ions, or a combination thereof pass through the second layer of the second material to interact with the two dimensional material, the interaction of ions, neutralized ions, or a combination thereof with the first material introducing a plurality of defects in the first material and the interaction of at least a portion of the ions, neutralized ions, or a combination thereof with the second material promoting expansion of the defects into holes.

23. The process of claim 22, wherein the second material interacts with the ions, neutralized ions, or a combination thereof to produce fragments of the second material, at least some of the fragments of the second material being directed towards the first material.