WO2017156297A2

WO2017156297A2 - Hybrid graphene materials and methods of fabrication

Info

Publication number: WO2017156297A2
Application number: PCT/US2017/021614
Authority: WO
Inventors: Robert Terry KENNON; Deepak Varshney; Michael R. Johnson; Scott V. Johnson; Benjamin J. WEINER; Peter J. BORGHETTI
Original assignee: Advanced Green Innovations, LLC
Priority date: 2016-03-11
Filing date: 2017-03-09
Publication date: 2017-09-14
Also published as: WO2017156297A3

Abstract

Methods for fabricating graphene materials may coat a hydrocarbon precursor onto a metal substrate and heat the coated metal substrate to a first temperature. Methods may then maintain the first temperature of the coated metal substrate for a duration which dissociates the hydrocarbon precursor into carbon on the metal substrate, and cool the coated metal substrate to a second temperature that is lower than the first temperature. Heating the coated metal substrate may dissociate the hydrocarbon precursor and cooling the coated metal substrate may allow the dissociated hydrocarbon to arrange itself into graphene on the metal substrate. The present invention comprises a method of fabricating graphene (2D and 3D) structures, doped graphene, graphene-nanoparticle hybrid, graphene nanostructure hybrids using semisolid hydrocarbons in the absence of any gaseous precursors as well as method for forming multiple graphene patterns and transfer of the graphene patterns from the substrate to a transfer strip.

Description

HYBRID GRAPHENE MATERIALS AND METHODS OF FABRICATION

CROSS-REFERENCE TO RELATED APPLICATION

[0001] This application is a PCT international application of U.S. Non-provisional Application Serial No. 15/068,269, filed on March 11 , 2016, titled Hybrid Graphene Materials and Methods of Fabrication, and also claims priority to U.S. Provisional Application Serial No. 62/453,925, filed on February 2, 2017, titled Hybrid Graphene Materials and Methods of Fabrication, both are incorporated herein by reference in their entirety.

TECHNICAL FIELD

[0002] This patent document relates to systems, devices, and processes that use nanoscale fabrication technologies.

BACKGROUND

[0003] Graphene is an allotrope of carbon which takes the form of an ordered hexagonal lattice of carbon atoms with sp²-hybridized bonds. The hexagonal lattice may present as a single layer (with a thickness of one carbon atom) or multiple sheets ordered three-dimensionally. It is the fundamental structural element for other carbon ailotropes, including graphite and carbon nanotubes. The former consists of randomly stacked graphene layers while the latter is essentially a section of graphene rolled to form a hollow cylinder. Graphene has many singular and/or extraordinary properties. Its electrical and thermal conductivities are among the highest of all materials making it an excellent candidate for (nano) electronics applications. Graphene's mechanical strength is significantly greater than steel, offering great potential for structural applications given a suitable process for its large-scale, efficient fabrication.

[0004] Nanotechnology provides techniques or processes for fabricating structures, devices, and systems with features at a molecular or atomic scale, e.g., structures in a range of about one to hundreds of nanometers in some applications. For example, nanoscale devices can be configured to include sizes similar to some large molecules, e.g., biomolecules such as enzymes. Nano-sized materials used to create a nanostructure, nanodevice, or a nanosystem can exhibit various unique

i properties, particularly those properties based on quantum mechanical effects including optical properties, that are not present in the same materials at larger dimensions. Such unique properties can be exploited for a wide range of applications.

SUMMARY

[0005] Graphene materials and methods to produce the graphene materials are disclosed, including systems and devices implementing the methods to fabricate graphene materials.

[0006] The subject matter described herein may be implemented to provide one or more of the following features. For example, the disclosed technology includes a method of fabricating graphene in 2D and 3D structures, including graphene sheets (2D structure), graphene foam (3D structures), graphene-hybrid nanostructures, and doped graphene. In some embodiments, the disclosed fabrication methods can include using a precursor comprising semisolid saturated hydrocarbons, or a mixture of different hydrocarbons, for the growth of graphene on 2D substrates and/or 3D metal substrates, a mixture of hydrocarbons together with dopants for doped graphene, and/or a mixture of hydrocarbons together with semiconducting nanoparticles, and/or metal nanoparticles, and/or insulating nanoparticles. Using thermal decomposition and other processes, graphene and graphene-hybrid nanostructures may be fabricated.

[0007] In some embodiments, the substrate may include pre-annealed or un- annealed nickel (Ni), copper (Cu), stainless steels, or aluminum foil, rectangular or rolled nickel, copper, or stainless steel foam, and any of the following metals: cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), sapphire (AI2O3), chromium (Cr), copper (Cu), germanium (Ga), gallium arsenide (GaAs), gallium nitride (GaN), magnesium (Mg), manganese (Mn), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V), zirconium (Zr), and other suitable metals. Too, the substrate may be a non-metal, such as silicon and mica, that includes a layer of metal upon which the precursor is coated. Some embodiments of the substrates can act as a catalyst, while other substrates are non-catalyst substrates and the catalyst is applied to the non-catalyst substrate. [0008] In some embodiments, the precursor may include n-tetracosane and/or n- octacosane, paraffin, paraffin melt, candle wax, white petrolatum, or other hydrocarbons and semisolid saturated hydrocarbons. The precursor may be used as a seeding mixture together with any dopant or metal nanoparticles for the fabrication of the graphene nanoparticles, the graphene-hybrid nanostructures, and/or nitrogen-, boron-, sulfur- containing materials or other dopants.

[0009] One embodiment described herein may include a method for fabricating graphene materials. The method may coat a semisolid non-volatile hydrocarbon precursor onto a metal substrate and then heat the coated metal substrate to a first temperature. The method may then maintain the first temperature of the coated metal substrate for a duration which dissociates the semisolid hydrocarbon precursor into carbon on the metal substrate, and cool the coated metal substrate to a second temperature that is lower than the first temperature. Heating the coated metal substrate may dissociate the semisolid hydrocarbon precursor and cooling the coated metal substrate may allow the dissociated hydrocarbon to arrange itself into graphene on the metal substrate.

[0010] Another embodiment described herein may include a method for producing porous graphene. The method may include coating a non-volatile semisolid hydrocarbon-nanoparticle mixture onto a metal substrate. The hydrocarbon- nanoparticle mixture may include a semisolid saturated hydrocarbon and nanoparticles. The nanoparticles may include at least one of copper, nickel, activated carbon, silicon, zinc oxide, tin oxide, or manganese oxide. The method may also heat the semisolid hydrocarbon-nanoparticle mixture coated metal substrate to substantially at least 450°C and maintain a temperature of the hydrocarbon- nanoparticle mixture coated metal substrate at substantially at least 450°C. Maintaining the temperature at substantially at least 450°C may dissociate the hydrocarbon-nanoparticle mixture on the surface of the metal substrate into carbon and the nanoparticles. The method may then cool the heated hydrocarbon- nanoparticle mixture coated metal substrate by substantially at least 20°C per minute to reach 200°C or less. The cooling may allow the carbon to precipitate out at the surface of the metal substrate or otherwise arrange itself into graphene together with the nanoparticles. The method may also coat a polymer on the graphene and nanoparticles and then disperse the metal substrate and nanoparticles.

[0011] Another embodiment of the present invention provides methods of fabricating graphene-nanoparticle hybrids, graphene-nanostructure hybrids, and doped graphene, or any combination thereof, using a seeding mixture comprising semisolid hydrocarbons and one or more of semiconducting nanoparticles, and/or metal nanoparticles, and/or insulating nanoparticles, by means of a thermal decomposition process. One embodiment of the present invention uses white petrolatum seeding mixture together with any dopant or metal nanoparticles for the fabrication of graphene-nanoparticle, doped graphene or graphene-nanostructure hybrids.

[0012] The fabrication process can be batch (for example, static), semi-continuous (for example, timed incremental advancement of the substrate through the heating- cooling zones), or continuous (constant movement of the substrate through the heating-cooling zones).

[0013] Potential Applications of the present invention include, for illustration purpose only and not to limit the invention, are:

[0014] A. Hydrogen storage

[0015] B. Photovoltaic devices

[0016] C. Fuel cells

[0017] D. Supercapacitors

[0018] E. Gas separation membranes

[0019] F. High temperature electronics

[0020] G. Li-ion batteries

[0021] H. Superconductors

[0022] I. Catalyst support [0023] J. Chemical sensors

[0024] One or more of the present inventions solve the following problems:

[0025] A. The graphene material of the present invention will cover a vast surface area

[0026] B. Easy fabrication of doped graphene

[0027] C. Easy fabrication of metal nanoparticle incorporated graphene structures [0028] D. Single step synthesis

[0029] The graphene/carbon nanotube (Gr/CNT) hybrids of the present invention will have extraordinary physical properties and promising engineering applications because of the placement of CNTs among graphene planes through covalent C-C bonding.

[0030] The proposed nanostructure would combine adsorptive and transport properties of both species, leading to a stable, chemically uniform 3-D network. Carbon nanotube-graphene hybrids can be used to separate H₂ from gas mixtures.

BRIEF DESCRIPTION OF THE DRAWINGS

[0031] The figures described below depict various aspects of the methods, systems, and devices disclosed herein. It should be understood that each figure depicts an embodiment of a particular aspect of the disclosed methods, systems, and devices, and that each of the figures is intended to accord with a possible embodiment thereof. Further, wherever possible, the following description refers to the reference numerals included in the following figures, in which features depicted in multiple figures are designated with consistent reference numerals.

[0032] Figure 1 shows an illustrative process diagram of an exemplary graphene synthesis method;

[0033] Figure 2 shows a further illustrative process diagram of the exemplary graphene synthesis method; [0034] Figure 3 show exemplary cooling rate effects of graphene synthesis methods;

[0035] Figure 4 shows a still further illustrative process diagram of an exemplary graphene synthesis method;

[0036] Figure 5 shows an illustrative process diagram of an exemplary graphene synthesis method to produce tubular graphene membranes;

[0037] Figures 6A, 6B, 6C, and 6D show exemplary methods for fabricating carbon nanotube structures;

[0038] Figures 7A1 , 7A2, 7 A3, 7B1 , 7B2, 7B3, 7C1A-C, 7C2, 7C3, 7C4A-E, 7D1A- C, 7D2, 7D3, 7E1 , 7E2, 7E3, 7F1 , 7F2, 7G1A-B, 7G2A-B, and 7G3A-E show results of working examples of the methods described herein;

[0039] Figures 8A-E are flow diagrams of the fabrication methods of fabricating graphene-nanoparticle, graphene-nanostructure hybrid structure and doped graphene using a seeding mixture comprising semi solid hydrocarbons and, and nanoparticles, metal nanoparticles using thermal decomposition;

[0040] Figure 8F is a pictorial representation of one embodiment of the present invention illustrating the nanoparticles and precursor (e.g., saturated hydrocarbon) being applied directly to the substrate without the step of incorporating nanoparticles into a melt to form a liquefied mixture that is applied to the substrate;

[0041] Figures 9A-D4 show results of working examples of another method described herein of nitrogen-doped graphene;

[0042] Figure 10 shows results of working examples of another method described herein of nitrogen-incorporated graphene;

[0043] Figures 11A1-C2 show results of working examples of another method described herein of nanostructure-graphene hybrid material, where nanostructures include nanotubes, nanorods, nanowires, quantum dots, and nanoflakes;

[0044] Figure 12 shows a test specimen that is a 1 inch by 1 inch copper foil substrate with 4 mg of semisolid precursor;

[0045] Figures 13A-R shows results of working examples of continuous manufacturing process to grow graphene;

[0046] Figures 14A-E show results of working examples of another method described herein of a diamond-graphene hybrid;

[0047] Figures 15A-B illustrate another embodiment of the present invention where a CVD process uses nanostructure forming precursor gasses are passed over a metal incorporated graphene sheet to form 3D nanostructures on the graphene sheet;

[0048] Figures 16A-17E show illustrations of embodiments of continuous manufacturing process systems; and

[0049] Figure 18 shows an illustration of one embodiment of the present invention for graphene formation during an extrusion process.

DETAILED DESCRIPTION

[0050] Techniques, systems, and devices are described for fabricating graphene materials and graphene-hybrid nanostructured materials.

[0051] In some aspects, the disclosed technology provides methods of fabricating graphene 2D and 3D structures, doped graphene 2D and 3D structures, and graphene incorporated with metal, and/or semiconducting, and/or insulating nanoparticles using semisolid saturated hydrocarbons or their mixtures, among other materials, in some implementations, metal, and/or semiconducting, and/or insulating nanoparticles embedded graphene films can be fabricated and further used as substrates or templates for the growth of various kind of nanomaterials and combinations thereof, e.g., resulting in graphene-nanomaterial heterostructure. In some implementations, for example, dopant utilized in the fabrication methods can include lithium, beryllium, boron, nitrogen, phosphorous, or their compounds. In some embodiments, the disclosed methods include single-step synthesis processes.

[0052] In some aspects, the disclosed technology provides methods of fabricating the nanoparticle-incorporated graphene 2D and 3D structures (graphene- nanomaterial incorporated structure), e.g., including, but not limited to, Si incorporated graphene, Cu incorporated graphene, Au incorporated graphene, among others.

[0053] In some aspects, the disclosed technology provides methods of fabricating graphene hybrid 2D and 3D structures, e.g., such as carbon nanotube-graphene, boron nitride nanotube-graphene, semiconductor oxide nanostructures, carbon nanofibers, and their combination. The disclosed technology provides methods of fabricating graphene-nanomaterial heterostructure, e.g., such as graphene-carbon nanotube heterostructure, and graphene-semiconductor oxide nanostructure heterostructure (e.g., such as graphene-Sn02 nanorods, graphene-Si nanowires heterostructure).

[0054] In some aspects, the disclosed technology provides methods of fabricating doped graphene films using semisolid saturated hydrocarbon mixture and at least one dopant.

[0055] Various and exemplary aspects of the present technology include, but are not limited to doped graphene, nanoparticle incorporated graphene, graphene- nanostructure hybrids, doped graphene-nanostructure hybrids that can be used for various applications like fuel cell, super capacitors, catalyst support, photovoltaic devices, chemical sensors and gas separable membranes.

[0056] Exemplary applications of the present technology include, but are not limited to: hydrogen storage; photovoltaic devices; fuel ceils; super capacitors; gas separable membranes; high temperature electronics: Li ion batteries; catalyst support; and chemical sensors; among others.

[0057] The disclosed technology is capable of being implemented to provide the following. For example, the produced graphene material can be fabricated to have a vast surface area. For example, the disclosed fabrication methods can allow for easy fabrication of doped graphene. For example, the disclosed fabrication methods can allow for easy fabrication of metal nanoparticle incorporated graphene structures. For example, the disclosed fabrication methods can allow for single step synthesis.

[0058] Conventional fabrication methods are incapable of producing different graphene-hybrid nanostructures in a single fabrication step. In contrast, the disclosed technology includes methods of fabrication of graphene-hybrid nanostructures in a single synthesis step or process.

[0059] The methods described herein are different from past processes to produce graphene and provide various advantages. For example, the methods described herein employ an environment free of gaseous Hydrocarbon precursors for the production of graphene structures where no hazardous or poisonous gasses are used. Further, growth time is reduced and, beyond a furnace, no specialized equipment is needed providing a cost-effective, environmentally friendly method for producing graphene structures. Using the methods described herein, a wide range of graphene and graphene hybrid materials and structures may be produced. While not an exhaustive listing, materials such as 2D graphene sheets, 3D graphene foam, graphene hybrid materials and structures employing various other materials (e.g., nanoparticles of silicon, copper, iron, gold having a size of 100nm or about 100nm or less), activated carbon (e.g., activated carbon nanopowder having specific surface area of about 1000 m²/gm), graphene-carbon nanotube hybrid structures), and doped graphene materials such as nitrogen-doped graphene. Other materials and structures may be fabricated employing the methods herein described including graphene platinum, palladium, or manganese hybrid materials and structures, layered structures of graphene nanotubes, silicon nanowires, graphene-quantum dots hybrid structures, and graphene-metal oxide semiconductor (MoS) hybrid structures. Still other materials and structures may be fabricated employing the methods herein described including graphene-gold nanoparticles hybrid on nickel foam and foils, graphene-iron nanoparticles hybrid on nickel foam and foils, graphene-nickel nanoparticles hybrid on nickel foam and foils, a sheet, a deposited layer, nitrogen-doped graphene-porous silicon nanoparticles hybrid, nitrogen-doped graphene-iron nanoparticles hybrid on nickel foam, graphene copper/zinc oxide hybrid on nickel foam, graphene-Ri2o (Cu/ZnO/A Oa) hybrid on nickel foam and foils, graphene-CNT hybrid structure on nickel foam, and graphene-coated stainless steels wire.

[0060] In one exemplary embodiment, a method to fabricate graphene can include the following preparation procedures in a single process. The single-step synthesis method includes a heating-cooling process of a semisolid non-volatile hydrocarbon or their mixtures that are coated on a substrate before being placed in a furnace for heating and processing into graphene. For example, a semisolid non-volatile saturated hydrocarbon having single bonds and containing the maximum number of hydrogen atoms for each carbon atom may be used. White petrolatum (petroleum jelly), paraffin, paraffin melt, and other materials may be used as an inexpensive precursor. In some embodiments, a precursor containing at least twenty carbon atoms is used.

[0061] Exemplary preparation procedures to implement the single-step synthesis method can include coating the semisolid hydrocarbon or other precursor having at least twenty carbon atoms on the (2D or 3D) metal substrates (e.g. , HI, Cu etc.) and subjecting the coated substrate to a heating-cooling thermal process. In some implementations, the exemplary thermal process can include putting the coated-metal substrate (e.g., hydrocarbon coated Ni foil) in a tube furnace and preparing the environment for graphene growth (e.g., pumping down the furnace to a base pressure to 5 mTorr or less and purging the environment) and heating the furnace containing the semisolid hyd roca rbo n-coated substrate to an elevated temperature. The elevated temperature may be high enough to dissociate the semisolid non-volatile, saturated hydrocarbon. In some embodiments, the coated substrate may reach substantially at least 450°C. In some implementations, the exemplary heating-cooling process can include, at the elevated temperature (at least 450°C), providing a non-reactive gas (e.g., Na and/or Ar) to maintain the pressure to an increased pressure from the base pressure (e.g., substantially at least 10 mTorr) for a time duration, depending on the type of substrate used. In some embodiments, the temperature for disassociating the carbon from the semisolid non-volatile hydrocarbon is substantially at least 15 sec. In some implementations, after the desired time required for growth (at least 15 sec), the exemplary heating-cooling thermal process can include lowering the furnace temperature to a second elevated temperature at a particular cooling rate for the growth of graphene. In some embodiments, the elevated temperature is lowered to at least 200X at a cooling rate in the range 20°C /min -100 °C /min.

[0062] In another exemplary embodiment, a method to fabricate nitrogen-doped graphene can include the following preparation procedures in a single process. This single-step synthesis method includes a heating-cooling thermal process of a hydrocarbon-nitrogenous compound mixture coated on a metal substrate. Exemplary preparation procedures to implement the single-step synthesis method can include providing the 2D or 3D substrates (e.g., Ni, Cu, stainless steels, etc.); providing a semisolid, non-volatile, saturated hydrocarbon or mixtures thereof (e.g., which can be configured to include tetracosane and octacosane melt or materials such as paraffin and petrolatum); and adding at least one chemical compound including nitrogen as one of the elements (nitrogenous compound) to this mixture, e.g., such as pyridine, phthalocyanine, or other compound. Exemplary preparation procedures to implement the single-step synthesis method can include coating the semisolid hydrocarbon- nitrogenous compound mixture on the (2D or 3D) metal substrate (e.g. Ni, Cu, stainless steels). In some implementations, the exemplary heating-cooling thermal process can include putting the coated-metal substrate (e.g., hydrocarbon coated Ni foil) in a tube furnace, and preparing the furnace by pumping down the furnace to the base pressure (at least 5 mTorr) and heating the furnace to the elevated temperature (at least 450° C). In some implementations, the exemplary heating-cooling process can include, at the elevated temperature (at least 450°C), providing a non-reactive gas (e.g., N2 and/or Ar, etc.) to maintain the pressure to an increased pressure from the base (e.g., at least 1 mTorr) for a time duration (e.g., at least 15 sec). In some implementations, after the desired time required for growth (e.g., at least 15 sec), the exemplary heating-cooling thermal process can include lowering the furnace temperature (at least 200°C) at a particular cooling rate (at least 20°C/min) for the growth of nitrogen-doped graphene.

[0063] In another exemplary embodiment, a method to fabricate metal, and/or semiconducting, and/or insulating nanoparticle-incorporated graphene can include the following preparation procedures in a single process. This single-step synthesis method includes a heating-cooling process of a semisolid, non-volatile, saturated hydrocarbon and metal, metalloid, and/or semiconductor nanoparticle-mixture coated on a substrate. Exemplary preparation procedures to implement the single-step synthesis method can include providing the 2D or 3D metal substrate (e.g., Ni, Cu, stainless steels, etc.); providing a semisolid, non-volatile, saturated hydrocarbon or other mixture (e.g. , which can be configured to include tetracosane and octacosane melt); and adding metal, metalloid, and/or semiconductor nanoparticles to this mixture. For example, the metal nanoparticles can include nickel, copper, iron, gold, silver, platinum, palladium, and/or cobalt, iridium, rhodium, osmium, and ruthenium among other metal nanoparticles; and, for example, the semiconductor nanoparticles can include silicon, zinc oxide, tin oxide, and/or manganese oxide, among other semiconductor nanoparticles. Exemplary preparation procedures to implement the single-step synthesis method can include coating the semisolid hydrocarbon- nanoparticle mixture on the metal substrate (e.g., Ni, Cu, stainless steels). In some implementations, the exemplary heating-cooling process can include putting the coated- metal substrate (e.g., Ni, Cu, stainless steels) in a tube furnace, and pumping down the furnace to the base pressure (at least 5 mTorr) and heating the furnace to an elevated temperature (at least 450°C). In some implementations, the exemplary heating-cooling process can include, at the elevated temperature (at least 450°C), providing a gas (e.g., N2 and/or Ar) to maintain the pressure to an increased pressure from the base (at least 1 mTorr) for a time duration, at least 15 sec. In some implementations, after the desired time required for growth (at least 15 sec), the exemplary heating-cooling process can include lowering the furnace temperature to a second elevated temperature at a particular cooling rate for the growth of metal, and/or semiconducting, and/or insulating nanoparticle-incorporated graphene. In some embodiments, the elevated temperature may be reduced to 200°C at a at a cooling rate ranging between 20-100°C/min.

[0064] In another exemplary embodiment, a method to fabricate metal, and/or semiconducting, and/or insulating nanoparticle-incorporated and nitrogen-doped graphene can include the following preparation procedures in a single process. This single-step synthesis method includes a heating-cooling thermal process of a hydrocarbon (e.g., a semisolid saturated hydrocarbon), a metal, metalloid, and/or semiconductor nanoparticle, and nitrogenous compound-mixture coated on a substrate. Exemplary preparation procedures to implement the single-step synthesis method can include providing the 2D or 3D metal substrates (e.g., Ni, Cu, stainless steels); preparing a hydrocarbon (e.g., a semisolid saturated hydrocarbon or other mixture which can be configured to include tetracosane and octacosane melt); adding at least one chemical compound including nitrogen as one of the elements (nitrogenous compound) to this mixture (e.g., pyridine, phthalocyanine, pyrazole, etc.); and adding metal, metalloid, and/or semiconductor nanoparticles to this mixture. Exemplary preparation procedures to implement the single-step synthesis method can include coating the semisolid hydrocarbon-nanoparticle-nitrogenous compound mixture on the 2D or 3D metal substrate (e.g., Ni, Cu, stainless steels foil). In some implementations, the exemplary heating-cooling process can include putting the coated-metal substrate (e.g., semisolid hydrocarbon coated Ni, Cu, stainless steels) in a tube furnace, and pumping down the furnace to the base pressure (at least 5 mTorr) and heating the furnace to an elevated temperature (at least 450°C). In some implementations, the exemplary heating-cooling process can include, at the elevated temperature (at least 450°C), providing a gas (e.g., N2 and/or Ar) to maintain the pressure to an increased pressure from the base (at least 1 mTorr) for a time duration, at least 15 sec. In some implementations, after the desired time required for growth (e.g., at least 15 sec), the exemplary heating-cooling process can include lowering the furnace temperature to a second elevated temperature at a particular cooling rate for the growth of metal, and/or semiconducting, and/or insulating nanoparticle- incorporated and nitrogen-doped graphene. In some embodiments, the elevated temperature may be reduced to at least 200°C at a rate ranging from about 20- 100°C/min.

[0065] Figure 1 shows an illustrative process diagram of an exemplary graphene synthesis method 100 and Figure 2 illustrates fabrication of graphene using the method 100 of figure 1. At step 102 (figure 1 ), a substrate material 202 (figure 2) may be cleaned. In some embodiments, cleaning may include an ultrasonic process lasting fifteen to thirty minutes using acetone, propanol, or other agent. In other embodiments, cleaning may include electro-polishing or another chemical cleaning method. At step 104, a semisolid hydrocarbon precursor 204 (e.g., a semisolid non-volatile, saturated hydrocarbon or other mixture) may be applied to the substrate material 202. The coating of the coated substrate 206 may comprise a paraffin melt, petrolatum, or other semisolid, non-volatile, saturated hydrocarbon precursor 204 coated on a nickel or copper foil or foam, a sheet, and a deposited layer or any other of the substrates as herein described. The coated substrate 206 may be heated in a furnace. In some embodiments, the coated substrate 206 may be placed in a process tube of a tube furnace at step 106. At step 108, a pressure within the process tube within the tube furnace may be reduced. In some embodiments, the pressure may be reduced to a base pressure for a period of time to prepare the furnace and coated substrate 206 for graphene growth. The base pressure may include a pressure of less than SOmTorr and the time period may include at least 15 minutes. In some embodiments, the base pressure includes a pressure of SmTorr or less. At step 1 10, the pressure within the process tube may be increased to a growth pressure. In some embodiments, the growth pressure is at least l OmTorr. At step 112, the tube furnace may heat the process tube and the coated substrate 206 at a particular rate to cause the carbon to dissociate from the precursor. In some embodiments, the tube furnace may heat the coated substrate 206 to at least 450°C at a heating rate of at least 20°C per minute and cause the semisolid hydrocarbon precursor 204 to dissociate on the substrate 202 to form carbon 208. In other embodiments, the furnace may be heated to between about 800°C and about 1000°C at a heating rate of about 20°C per minute. For example, the temperature of the furnace may be increased to a higher temperature (at least 450°C or about 800°C to about 1000°C), which results in the dissociation 106 of the carbon precursor into carbon at high temperature on the substrate surface 104. At step 1 14, the temperature of the furnace may be maintained for a duration. In some embodiments, the duration includes a time of at least 15 seconds to about 38 minutes or until the carbon 208 is dissociated on the metal substrate. At step 116, the temperature of the coated metal substrate is reduced by cooling at a cooling rate to a desired temperature. In some embodiments, the cooling rate includes a rate of at least 20°C per minute and the desired temperature includes 200°C or less. On cooling, carbon precipitates out at the surface of the catalyst and arranges in hexagonal structures 212 (graphene). At step 1 18, once the furnace reaches the desired temperature, the pressure of the furnace may be increased to atmospheric in order to remove the sample.

[0066] In some embodiments, the process described above and in association with any of the other forms of graphene and graphene-hybrid materials described herein may employ a series of steps within a furnace that each include a time, temperature, and pressure. For example, over a period of about 36 minutes, the coated substrate 206 may be heated from 25°C or about 25°C to 1000°C or about 1000°C at a pressure of about SOOmTorr or less. The coated precursor may then be held at about 1000°C for about 30 minutes at the 500mTorr or less pressure. Over a period of about 12 minutes, the coated precursor 206 may then be cooled to about 750°C and the pressure changed to about 50mTorr. Then, over a period of about 30 minutes, the coated substrate may be "flash cooled" to about 200°C at the pressure of about 50mTorr. In further embodiments, the processes described herein may occur at atmospheric pressure.

[0067] Figure 3 shows an illustrative process diagram of exemplary cooling rate effects 300 of the graphene fabrication methods described herein (e.g., step 116 of the method 100). At a fast cooling rate 302, where the cooling rate is greater than about 100°C/min, for example, carbon atoms 304 that dissociate in the substrate 306 may not get enough time to precipitate out from the surface as a result of fast cooling, and only few carbon atoms may precipitate out from the substrate surface, which may not be enough to form a graphene structure 212. At a medium cooling rate 308, where the cooling rate which is in the range of about 20-100°C/min, the carbon atoms that dissociate in the substrate due to high temperature (e.g., at steps 1 12 and 1 14 of method 100) may receive enough time to precipitate out from the surface and arrange themselves in the form of graphene 212. At a slow cooling rate 310, where the cooling rate which is slower than 20°C/min, the carbon atoms 312 that dissociate in the exemplary Nickel substrate may receive enough time to arrange themselves in the Nickel, but may not precipitate out of the surface. As described herein, the cooling rate to form graphene is in the range of about 20-100°C/min.

[0068] Other exemplary graphene material fabrication techniques following the methods described herein may follow the same growth mechanism as generally described by the method 100. For example, the method 100 of Figure 1 may be followed in the growth of various engineered graphene materials including (i) nitrogen- doped graphene, (ii) metal, and/or semiconducting, and/or insulating nanoparticle- incorporated graphene, (iii) and/or metal, and/or semiconducting, and/or insulating nanoparticle-incorporated and nitrogen-doped graphene, and (iv) other graphene- nanostructure hybrids.

[0069] In some implementations of the disclosed methods, for example, the substrate 202, 306 can include copper foil, which can provide further uniformity in the formation of graphene layers. In further implementations, functionalization of the produced graphene or graphene-hybrid materials can be performed, and various activation processes can be included and implemented to activate the fabricated structure to increase the specific surface area required for certain exemplary applications.

[0070] Figure 4 shows an illustrative process diagram of an exemplary graphene synthesis method 400 to produce graphene which may be employed as gas separable membranes. Implementations of the exemplary method 400 can be used to fabricate porous graphene using exemplary nanoparticle-incorporated graphene, e.g., which can be produced using the method 100 of Figure 1. As shown in Figure 4, the method 400 includes coating a semisolid hydrocarbon-nanoparticle mixture 402 on a substrate or catalyst 408. The semisolid hydrocarbon mixture may include a precursor of saturated hydrocarbons 404 and metal nanoparticles 406 such as copper, nickel, etc. nanoparticles on the metal substrate 408) at 410. At 412, the semisolid hydrocarbon- nanoparticle coated substrate may be placed in a furnace (e.g., such as tube furnace). In the furnace, the temperature of the mixture 402 and substrate 404 may be increased to a higher temperature (e.g., at least 450°C) leaving carbon 416 and metal nanoparticles 406 on the substrate 408. Further, at the higher temperature, the semisolid saturated hydrocarbon carbon precursor 404 may be dissociated on the substrate surface, e.g., leaving the metal nanoparticles 406 at the surface at 418. In some implementations, the temperature of the furnace may be maintained for a desired duration to cause carbon dissolution into the substrate 408. At 420, the temperature of the furnace may be reduced by cooling at a desired cooling rate to a desired temperature. In some embodiments, the cooling rate is between 20-100°C per minute. On cooling, carbon precipitates out at the surface of the catalyst 404 and arranges themselves in hexagonal structures (graphene 422) together with metal nanoparticle incorporation 424.

[0071] At 426, the method 400 may coat a thin layer of polymer material 428 on the graphene and nanoparticle material. In some embodiments, the polymer includes Poly (methyl methacrylate) or PMMA. The polymer may be spin coated on the material to support the graphene. In other embodiments, the polymer may be drop cast and baked on the graphene. Further, the polymer may be treated, e.g., cleaned in hot acetone for a period of time, before using to coat the graphene. Likewise, the graphene may be treated prior to coating by thermal annealing within or outside of a vacuum. At 430 and 432, the method 400 may disperse the polymer-graphene/nanoparticle substrate (e.g., the exemplary PMMA-graphene-Ni or Cu substrate) in a chemical solution and at 434 may etch the substrate and the metal nanoparticles. A result of this etching is porous graphene 434.

[0072] Figure 5 shows an illustrative process diagram of an exemplary graphene synthesis method 500 to produce tubular graphene membranes. As shown in the schematic of Figure 5, a substrate 502 in the form of tube can be used, in some embodiments, the substrate 502 may comprise any of the materials (i.e., Ni, Cu, etc.) as herein described. End caps 504A, 504 B may be used to close the tube. The method 500 may include a process to coat the tubular substrate 502 with a semisolid hydrocarbon or semisolid hydrocarbon mixture 506. In some embodiments, the hydrocarbon 506 includes a semisolid hydrocarbon or semisolid saturated hydrocarbon such as paraffin melt, petrolatum, etc., to coat the substrate 502. The method 500 can include a process, such as the heating process described in relation to the method 100, to heat the tubular substrate 502 and precursor 506 undergo thermal decomposition of the precursor at elevated temperatures. As in the method 100, the heating process of the method 500 may result in the fabrication of graphene 508 over the surface of the tubular substrate 502. As in the method 400 of Figure 4, graphene coated tube 510 can then be dipped, spin coated, or otherwise coated, with a polymer 512 so that the polymer supports the fabricated graphene 508. After this, for example, the ends 504A, 504B of the tube can be opened and then the open-ended tube 514 can be dipped in and etching solution (e.g. , FeC , etc.) to etch or dissolve the substrate tube 502 leaving only the graphene 508 in the form of tube supported by the polymer 512. The method 500 can be implemented to produce various layered structures. In some embodiments, various steps of the method 500 may be repeated, thus resulting in multiple layers of graphene (e.g., one layer, five layers, etc.) and a graphene-carbon nanotube hybrid structure.

[0073] Exemplary applications of the embodiments described herein include photovoltaic applications, fuel cell applications, catalyst support applications, chemical sensor applications, and others. A multi-layered graphene-carbon nanotube hybrid structure, as described above, may be used in photovoltaic applications. Further, different material quantum dots or metal nanoparticles decorated hybrid structure and different nanostructures can be fabricated on metal nanoparticle embedded graphene films may be used in various other applications.

[0074] In some embodiments, for fuel cell applications, exemplary graphene materials of the disclosed technology can be produced to have different dopants that can be used to improve the efficiency and hydrogen storage properties of graphene and its hybrid structure, different nanoparticles that can be used to increase the charging and discharging properties of supercapacitors, and different functionalizations for various applications.

[0075] In further embodiments, for catalyst support applications, fabrication of catalyst supported graphene and nitrogen doped catalyst supported graphene can be implemented, e.g., to increase the surface area required for the catalyst for steam methane reforming application.

[0076] In still further embodiments, for chemical sensor applications, exemplary graphene materials of the disclosed technology can be functionalized to provide specialized detection of specified analytes.

[0077] With reference to Figure 6A and 6B, in some aspects of the embodiments described herein, fabrication methods include producing vertically aligned carbon nanotubes 602 (VACNTs) with pores 604, where the pores 604 activate the carbon nanotubes.

[0078] Figure 6A shows an illustrative process diagram of an exemplary method 600 for producing a composite material formed of graphene and VACNTs, e.g., which can include porous VACNTs. One exemplary method 600 to produce composite materials including graphene and the VACNTs 602 includes coating a substrate 610 with a precursor material 606 including catalyst nanoparticles 608 embedded in the precursor material 606 on a substrate 610. In some embodiments, the substrate 610 may include a copper foil substrate or a nickel foil substrate, and the material 606 can include metal nanoparticles 608. The metal nanoparticles 608 may be patterned in the coating, e.g., using photolithography and/or etched holes in the substrate 610. Using chemical vapor deposition 612, the method 600 may apply and grow carbon nanotubes 602 over the coated film 614, in which the catalyst nanoparticles 608 are raised on the carbon nanotubes 602. In some embodiments, the nanotubes 602 are Vertically Aligned Single Wall Carbon Nanotubes (VASWCNTs). The method 600 may then remove the substrate 610.

[0079] Figure 6B shows one example of a method 650 for producing a 3D layered graphene composite structure 652 using VAC NTs 602. For example, the method 650 may stack the structures produced by the method 600 of Figure 6A to build the 3D layered graphene composite structure 652.

[0080] Figure 6C shows an illustrative process diagram of an exemplary method 660 to produce porous VAC NTs. At 662, the method 660 may grow carbon nanotubes 664 on a substrate 666. In some embodiments, the substrate 666 may include silicon. In other embodiments, the substrate 666 may include aluminum foil. At 668, the method 660 may form graphene 670 on a substrate 666 using a process as generally described at Figures 1 and 2. At 674, the method 660 may coat the graphene 670 with a polymer 676. in some embodiments, coating the graphene 670 at 674 may include spin coating a layer of Poly PMMA, Poly (dimethylsiloxane) (PDMS), or other polymer 676 onto the graphene 670. At 677, carbon nanotubes 664 may be grown on the substrate 666 as generally described with reference to the method 600 and Figure 6A. At 680, the carbon nanotubes 664 may be dipped in a solution 682. In some embodiments, the solution 682 may include a basic solution such as potassium hydroxide (KGH). In other embodiments, the solution 682 may include an acidic solution such as hydrogen chloride (HCI) alone or in combination with ferric chloride (FeC ). At 684, nanoparticles 684 of the solution 682 may become embedded into the nanotubes 664 as a result of step 680. In some embodiments of step 684, nanoparticles 684 of the substrate 666 (e.g., aluminum) may become embedded into the nanotubes 664 as a result of step 680. The nanoparticles may be sized to about 2nm and 50nm, At 686, the nanotubes 664 with embedded nanoparticles 684 of the solution 682 may be heated to evaporate any liquid portion of the solution and then annealed in a gaseous atmosphere to remove the nanoparticles 684 of the solution 682 from the nanotubes 664. In some embodiments, the gas for the annealing step may include argon (e.g., at a flow rate of about 120-150 standard cubic centimeters per minute), or other noble gas or an inert gas. Annealing at 686 may be completed in the absence of any hydrocarbon gas, using argon or other noble gas, an inert gas, or no gas at all. In some embodiments, a gas used in annealing may react with the nanoparticles 682 and result in porous carbon nanotubes 688. In other embodiments, annealing may be completed in the absence of any particular gas, where no gas is used in annealing, and where graphene growth may be completed over a period of about 30 to 45 seconds at a temperature of 900°C and a pressure of about 300mTorr.

[0081] With reference to Figure 6D, the various graphene and nanotube structures as described herein may be assembled to create a 3D layered graphene composite structure 690 having VAC NTs 692 of identical or varying diameters to provide gas separation of an input gas 694 to separate out one or more gas constituents as the output gas 696. In some embodiments, with reference to the methods 600, 650 of Figures 6A and 6B, identical or various sized nanoparticles 608 may be used in the growth processes to create identical or varied diameters of the carbon nanotubes 692, thus allowing the structure 690 to provide separation of identical or various-sized molecules from the input gas 694.

[0082] Figures 7A1-7F2 show some working examples of the subject matter described herein. These examples are in no way exhaustive of the possible results from the inventions described in this document and represent only some of the results that are possible. These examples illustrate the present inventions and some of its various embodiments and are not intended to limit the scope of the present invention in any way.

[0083] Figures 7A1 -7 A3 illustrate a working example of the fabrication of graphene sheets on copper foils. Saturated hydrocarbons n-tetracosane and n-Octacosane may be used. In a typical procedure, 1 g of n-Tetracosane (Alpha Aesar) and 1 g of n- Octacosane (Alpha Aesar) may be mixed and the mixture may be melted on a hot plate for 10 min and heated to a temperature of 120°C at a rate of 15°C/min. A small portion of this mixture (~0.05 g) may be transferred on to a copper foil (25 μητι- 250 μηη thick, Alpha Aesar) with the help of a glass dropper and allowed to cool to room temperature at a cooling rate of 15°C/min. The foil may then be placed in a quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 minutes. Then the pressure of the tube may be increased to 500 mTorr from base pressure. The temperature of the reactor may be fixed at 1000°C and the substrate placed at a temperature in the range of ^" 950-1000°C. A pressure in the range of 450-500 mTorr may be used and the sample placed in that condition for a duration of 18 min - 45 min. The reactor assembly may then be cooled to room temperature at a base pressure of < 5 mTorr.

[0084] Figures 7B1-7B3 illustrate a working example of the fabrication of graphene sheets on Nickel foils. Saturated hydrocarbons n-tetracosane (Alpha Aesar), and n- Octacosane (Alpha Aesar) may be used. In a typical procedure, 1 g of n-tetracosane and 1 g of n-Octacosane may be mixed and melted on a hot plate for 10 min. then heated to a temperature of 120°C at a rate of 15°C/min. A small portion of this mixture (-0.05 g) may be transferred on to a nickel foil (25 pm - 0.1 mm thick, Alpha Aesar) with the help of a glass dropper and allowed to cool to room temperature at a cooling rate of 15°C/min. The foil may then be placed in the quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 minutes. Then the pressure of the tube may be increased to 300 mTorr from base pressure. The temperature of the reactor may be fixed at 900°C and the substrate placed at a temperature in the range of approximately 800-900 °C. A pressure in the range of 250- 300 mTorr may be used and the sample placed in that condition for a duration from 15 seconds to 3 minutes. The reactor assembly may then be cooled to room temperature at a base pressure of < 5 mTorr.

[0085] Figures 7C1A-7C4E show the SE images of SiGr coated foam at low and high magnification showing the presence of the silicon nano particles (some individual and some are agglomerated) together with graphene coating illustrating the fabrication of silicon nanoparticles incorporated graphene. Saturated hydrocarbons, n- tetracosane (Alpha Aesar) and n-octacosane (Alpha Aesar) may be used to fabricate the required precursor material. In a typical procedure, 0.01 g of silicon nanoparticles (Alpha Aesar) may be mixed with 1g of n-tetracosane and 1g of n-octacosane and melted on a hot plate by heating the mixture to a temperature of 120°C at a rate of 15°C/min. A small portion of this mixture (~0.05 g) may be transferred on to a nickel foam (0.1 mm thick, Alpha Aesar) with the help of a glass dropper and allowed to cool to room temperature at a cooling rate of 15oC/min. The foil may then be placed in a quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 min, then the pressure of the tube may be increased to 300 mTorr from base pressure. The temperature of the reactor may be fixed at 900°C and the substrate placed at temperature in the range of approximately 800-900 °C. A pressure in the range of 250-300 mTorr may be used and the sample placed in that condition for a duration of 15 seconds - 3 minutes. The reactor assembly may then be cooled to room temperature at a base pressure of < 5 mTorr. Figures 7C4A-7C4E show the color EDX analysis of the image (a) showing the presence of nickel (substrate), carbon (graphene), silicon (Si nanoparticles) and oxygen (O).

[0086] Figures 7D1A-C, 7D2, and 7D3 may illustrate a working example of the fabrication of Nitrogen doped graphene. Saturated hydrocarbons, n-tetracosane (Alpha Aesar) and n-octacosane (Alpha Aesar) may be used to fabricate the required material. In a typical procedure, 0.01 g of Phthalocyanine (Alpha Aesar) may be mixed with 1g of n-tetracosane and 1g of n-octacosane and melted on a hot plate by heating the mixture to a temperature of 120°C at a rate of 15°C /min. A small portion of this mixture (~0.05 g) may be transferred on to a nickel foil (25 pm - 0.1 mm thick, Alpha Aesar) with the help of a glass dropper and allowed to cool to room temperature at a cooling rate of 15°C/min. The foil may then be placed in the quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 minutes. Then the pressure of the tube may be increased to 300 mTorr from base pressure. The temperature of the reactor may be fixed at 900°C and the substrate placed at temperature in the range of approximately 800-900°C. A pressure in the range of 250-300 mTorr may be used and the sample placed in that condition for a duration of 15 s - 3 min. The reactor assembly may then be cooled to room temperature at a base pressure of < 5 mTorr.

[0087] Figures 7E1 , 7E2, and 7E3 may illustrate a working example of graphene coated nickel foam (3D structure). Saturated hydrocarbons, n-tetracosane (Alpha Aesar) and n-octacosane (Alpha Aesar) may be used to fabricate the required material. In a typical procedure, 1g of n-tetracosane and 1g of n-octacosane may be mixed and melted on a hot plate by heating the mixture to a temperature of 120°C at a rate of 15°C/min. A small portion of this mixture (~0.05 g) may be transferred on to a 0.1 mm thick nickel foam (Alpha Aesar) with the help of a glass dropper and was allowed to cool to room temperature at a cooling rate of 15°C/min. The foil may then be placed in the quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 minutes. Then the pressure of the tube may be increased to 300 mTorr from base pressure. The temperature of the reactor may be fixed at 900°C and the substrate placed at temperature in the range of ^"800-900 °C. A pressure in the range of 250-300 mTorr may be used and the sample placed in that condition for a duration from 15 s - 3 min. The reactor assembly may then be cooled to room temperature at a base pressure of < 5 mTorr.

[0088] Figures 7F1 and 7F2 may illustrate a working example of the fabrication of a nanostructure-graphene hybrid in general and, particularly, a CNT-graphene hybrid structure. Saturated hydrocarbons, n-tetracosane (Alpha Aesar) and n-octacosane (Alpha Aesar) may be used to fabricate the required material. In a typical procedure, 0.01 g of commercially available carbon nanotubes (Nanostructured and Amorphous Materials Inc.) may be mixed with 1g of n-tetracosane and 1g of n-octacosane and melted on a hot plate by heating the mixture to a temperature of 120°C at a rate of 15°C /min. A small portion of this mixture (-0.05 g) may be transferred on to a nickel foam (0.1 mm thick, Alpha Aesar) with the help of a glass dropper and allowed to cool to room temperature at a cooling rate of 15°C/min. The foil may then be placed in the quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 minutes. Then the pressure of the tube may be increased to 300 mTorr from base pressure. The temperature of the reactor may be fixed at 900°C and the substrate placed at a temperature in the range of ^~ 800-900°C. A pressure in the range of 250-300 mTorr may be used and the sample may be placed in that condition for a duration of 15 s to 3 min. The reactor assembly may then be cooled to room temperature at a base pressure of <5 mTorr.

[0089] Figures 7G1A-B, 7G2A-B, and 7G3A-E illustrate a working example of the fabrication of Nitrogen doped graphene with metal nanoparticles incorporation. Saturated hydrocarbons, n-tetracosane (Alpha Aesar) and n-octacosane (Alpha Aesar) may be used to fabricate the required material. In a typical procedure, 0.01 g of copper phthalocyanine (Alpha Aesar) may be mixed with 1g of n-tetracosane and 1g of n-octacosane and melted on a hot plate by heating the mixture to a temperature of 120°C at a rate of 5°C/min. A small portion of this mixture (~0.05 g) may be transferred on to a nickel foam (0.1 mm thick, Alpha Aesar) with the help of a glass dropper and allowed to cool to room temperature at a cooling rate of 15°C/min. The foil may then be placed in the quartz tube. The tube may be pumped down to a base pressure (<5 mTorr) and kept at that pressure for 30 minutes. Then the pressure of the tube may be increased to 300 mTorr from base pressure. The temperature of the reactor may be fixed at 900 °C and the substrate placed at a temperature in the range of ^"800-900 °C. A pressure in the range of 250-300 mTorr may be used and the sample placed in that condition for a duration from 15 s - 3 min. The reactor assembly may then be cooled to room temperature at a base pressure of <5mTorr.

[0090] One embodiment of the present invention relates to a single-step process of fabricating doped graphene 2D and 3D structures including (i) graphene embedded with metal, or semiconducting, or insulating particles, (ii) metal, or semiconducting, or insulating particle incorporated doped graphene, and (iii) graphene nanostructure hybrid material using saturated hydrocarbons without masking or etching of the fabricated/grown graphene to pattern the dopants and/or nanoparticles.

[0091] The various aspects of this invention will include Doped graphene, nanoparticle incorporated graphene, graphene-nanostructure hybrids, doped graphene-nanostructure hybrids that can be used for various applications such as fuel cells, supercapacitors, catalyst support, photovoltaic devices, chemical sensors and gas separable membranes.

[0092] One embodiment of the present invention provides a method of fabricating doped graphene films using saturated hydrocarbon mixture and at least one dopant.

[0093] Another embodiment of the present invention provides a method of fabricating graphene doped graphene 2D and 3D structures and graphene embedded with metal, or semiconducting, or insulating particles using semisolid hydrocarbon e.g., White petrolatum. These metal, or semiconducting, or insulating particle embedded graphene films can be further used as substrates or templates for the growth of various kind of nanomaterials and combinations thereof, resulting in graphene-nanomaterial heterostructure. The dopant can be, but not limited to, lithium, beryllium, boron, nitrogen or their compounds.

[0094] Fabrication of doped graphene [0095] Now turning to Figure 8D illustrating the doped graphene fabrication process. Quantities of dopants vary up to the point whereby catalyzed growth of graphene is inhibited are combined with saturated hydrocarbons to form a combination (Step 1 D). The combination is heated to a predetermined temperature (40 °C -150 °C) obtain a melt, where varying the temperature controls the melting time and/or other properties of the melt (Step 2D). The melt is stirred or otherwise mixed to a mixture (Step 3D). In some embodiments, stirring or mixing may produce a substantially homogenous mixture. The mixture is transferred to a desired substrate (Step 4D). Non-limiting examples of desired substrates are nickel, copper, stainless steel, or germanium. The mixture is cooled to at least semisolid state to form a melt coated substrate (Step 5D). The coated substrate undergoes a chemical vapor deposition process (CVD) for the graphene growth (Step 6D). The coated substrate is in the presence of any inert gas (such as Ar, N2) at a substrate temperature in the range of 450-1000°C at a pressure from 1 mT to atmospheric pressure (Step 7D) to form metal incorporated doped graphene (Step 8D).

[0096] Fabrication of graphene embedded with metal, or semiconducting, or insulating nanoparticles

[0097] Now turning to Figure 8A illustrating the metal, or semiconducting, or insulating nanoparticles incorporated graphene fabrication process. Quantities of metal, or semiconducting, or insulating nanoparticles vary up to the point whereby catalyzed growth of graphene is inhibited are combined with saturated hydrocarbons to form a combination (Step 1A). The combination is heated to a predetermined temperature (40 °C -150 °C) obtain a melt, where varying the temperature controls the melting time and/or other properties of the melt (Step 2A). The melt is stirred or otherwise mixed to a mixture (Step 3A). In some embodiments, stirring or mixing may produce a substantially homogenous mixture. The mixture is transferred to a desired substrate (Step 4A). Non-limiting examples of desired substrates are nickel, copper, stainless steel, or germanium. The mixture is cooled to at least semisolid state to form a melt coated substrate (Step 5A). The coated substrate undergoes a chemical vapor deposition process (CVD) for the graphene growth (Step 6A). The coated substrate is in the presence of any inert gas (such as Ar, N2) at a substrate temperature in the range of 450-1000°C at a pressure from 1 mT to atmospheric pressure (Step 7 A) to form a sheet of Graphene embedded with metal, or semiconducting, or insulating particles (Step 8A).

[0098] CVD can include any of the following processes and equipment: Thermal CVD, Hot Filament Chemical Vapor Deposition (HFCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), and Micro Wave Plasma Enhanced Chemical Vapor Deposition (MWPECVD).

[0099] Saturated hydrocarbons are hydrocarbons for which the carbon atoms are connected by only single covalent bonds. They are the simplest class of hydrocarbons. They are called saturated because each carbon atom is bonded to as many hydrogen atoms as possible, in other words, the carbon atoms are saturated with hydrogen. Examples of suitable saturated hydrocarbons are Alkane hydrocarbons such as n- tetracosane and n-octacosane, or any semisolid hydrocarbon including petrolatum and petroleum jelly.

[00100] Fabrication of metal or semiconducting or insulating nanoparticle incorporated doped graphene

[00101] Now turning to Figure 8B illustrating the metal, or semiconducting, or insulating nanoparticles incorporated and doped graphene fabrication process. Quantities of metal, or semiconducting, or insulating nanoparticles and dopant vary up to the point whereby catalyzed growth of graphene is inhibited are combined with saturated hydrocarbons to form a combination (Step 1 B). The combination is heated to a predetermined temperature (40 °C -150 °C) obtain a melt, where varying the temperature controls the melting time and/or other properties of the melt (Step 2B). The melt is stirred or otherwise mixed to a mixture (Step 3B). In some embodiments, stirring or mixing may produce a substantially homogenous mixture. The mixture is transferred to a desired substrate (Step 4B). Non-limiting examples of desired substrates are nickel, copper, stainless steel, or germanium. The mixture is cooled to at least semisolid state to form a melt coated substrate (Step 5B). The coated substrate undergoes a chemical vapor deposition process (CVD) for the graphene growth (Step 6B). The coated substrate is in the presence of any inert gas (such as Ar, N2) at a substrate temperature in the range of 450-1000°C at a pressure from 1 mT to atmospheric pressure (Step 7B) to form a sheet of metal, or semiconducting, or insulating nanoparticle incorporated doped graphene (Step 8B).

[00102] Fabrication of graphene-nanostructure hybrid

[00103] Now turning to Figure 8C illustrating the graphene-nanostructure hybrid fabrication process. Quantities of nanostructure like CNTs vary up to the point whereby catalyzed growth of graphene is inhibited are combined with saturated hydrocarbons to form a combination (Step 1C). The combination is heated to a predetermined temperature (40 °C -150 °C) obtain a melt, where varying the temperature controls the melting time and/or other properties of the melt (Step 2C). The melt is stirred or otherwise mixed to a mixture (Step 3C). In some embodiments, stirring or mixing may produce a substantially homogenous mixture. The mixture is transferred to a desired substrate (Step 4C). Non-limiting examples of desired substrates are nickel, copper, stainless steel, or germanium. The mixture is cooled to at least semisolid state to form a melt coated substrate (Step 5C). The coated substrate undergoes a chemical vapor deposition process (CVD) for the graphene growth (Step 6C). The coated substrate is in the presence of any inert gas (such as Ar, N2) at a substrate temperature in the range of 450-1000°C at a pressure from 1 mT to atmospheric pressure (Step 7C) to form a graphene-nanostructure hybrid (Step 8C).

[00104] Now turning to Figure 8E that illustrates the process of applying the nanoparticles and precursor (e.g., saturated hydrocarbon) directly to the substrate without the step of preparing a melt of nanoparticles and precursor that will form a liquefied mixture applied to the substrate. Therefore, steps of other previously disclosed embodiments of the present invention (such as Steps 1-5 of Figures 8A-D) can be eliminated depending on the end-product application.

[00105] The following processes steps are illustrative and not intended to limit the invention or directives thereof:

[00106] Step 1 E: Provide a saturated hydrocarbon;

[00107] Step 2E: Provide an additive(s) selected from the group of meta(s)l/metalloid nanoparticles, nanostructures, and dopants; [00108] Step 3E: Provide a substrate;

[00109] Step 4E: Apply one or more layers of the saturated hydrocarbon to the substrate;

[00110] Step 5E: Apply one or more layers of the additive(s) to a top surface of the one or more layers of the saturated hydrocarbon;

[00111] Step 6E: Optionally apply additional layers of the saturated hydrocarbon to a top surface of the one or more layers of the additive(s);

[00112] Step 7E: Subject the one or more layers of the additive(s), the one or more layers of the saturated hydrocarbon, and the substrate to any inert gas (Ar, N₂) at a substrate temperature in the range of 450 °C to 1000 °C from 1 mT to atmospheric pressure.

[00113] Step 8E: Sheet of Graphene with incorporated additive(s) is formed

[00114] Now returning Step 6E, it can be further explained as additional steps. Some applications may require the application of additional layers of additives (such as metal, or semiconducting, or insulating nanoparticles, nanostructures, and dopants) applied on top of additional layers of precursor (such as saturated hydrocarbons). In such cases, one or more additional layers of the saturated hydrocarbon are applied to a top surface of the one or more layers of the additives, and then one or more additional layers of the one or more additives is applied to a top surface of the additional one or more layers of the saturated hydrocarbon after Step 5E and before Step 7E. These additional steps can be repeated before Step 7E until the desired layers of additive and precursor is achieved.

[00115] Figure 8F is a pictorial representation of the above described embodiment of the present invention illustrating the nanoparticles and precursor (e.g. , saturated hydrocarbon) being applied directly to the substrate without the step of transforming the nanoparticles and precursor into a melt to form a liquefied mixture that is applied to the substrate.

[001 6] To get uniformity in nanoparticle incorporated graphene, doped graphene or graphene nanostructure hybrids for different applications, the following variations can be implemented:

[00117] a) Fabrication of porous graphene using nanoparticle incorporated graphene.

[00118] b) Hybrid structure with different thickness of graphene layers (mono-, few- , multi-layer) can be fabricated.

[00119] c) Tubular graphene can be fabricated

[00120] d) Various activation processes can be used to activate the fabricated structure for the required applications.

[00121] e) Different layered structure from one layer to five layers graphene-carbon nanotube hybrid structure can be fabricated

[00122] f) Various quantum dots or metal nanoparticles hybrid structures can be fabricated.

[00123] g) Different nanostructures can be fabricated on metal nanoparticle- embedded graphene films.

[00124] h) Different dopants can be used to improve the efficiency and hydrogen storage properties of graphene and its hybrid structure.

[00125] i) Different nanoparticles can be used to increase the Charging and discharging properties of supercapacitors.

[00126] j) Different Functionalization will be done for the same.

[00127] Example 1 is an illustration of doped graphene.

[00128] The main features in the Raman spectra of pure graphene (Figure 9A) and Nitrogen doped (Figure 9B) grown by precursor of the present invention are the G band and D band, which lie at around 1582-1592 cnr¹ and 1340-1360 cm-¹, respectively. Another characteristic feature in graphene, the 2D band, appears at round 2700 - 2710 cm^"1. [00129] Comparison of Raman spectrum of N-doped graphene (NGr) and pure graphene

[00130] In case of pure graphene, D band is less intense (1355 cm-¹) where as in NGr it is of higher intensity (1365 cm-¹).

[00131] In case of pure graphene, G band is symmetrical whereas in NGr it is asymmetric

[00132] Figures 9C1-9C3 consist of SEM images of NGr showing the morphology of the film at low magnification and at higher magnification

[00133] Figures 9D1-9D4 show the color EDX of the image showing the presence of Nickel (substrate), carbon (graphene) and the Nitrogen (doping material). The Nitrogen signals are less as the time of acquisition of data is less.

[00134] Some advantages of the present invention process are as follows:

[00135] Easy to fabricate and cheap

[00136] large scale NGr is possible

[00137] No hazardous gases are required

[00138] 2D and 3D structures are possible

[00139] Any type (n-type, p-type) doping is achievable

[00140] Some of the applications for the present invention process are:

[00141] Water purification having Nitrogen-doped graphene nanosheets as reactive water purification membranes as described in an article authored by Yanbiao Liu et al. in Nano Research, July 2016, Volume 9, Issue 7, pp 1983-1993. Abstract: Oxidation of organic pollutants by sulfate radicals produced via activation of persulfate has emerged as a promising advanced oxidation technology to address various challenging environmental issues. The development of an effective, environmentally- friendly, metal-free catalyst is the key to this technology. Additionally, a supported catalyst design is more advantageous than conventional suspended powder catalysts from the point of view of mass transfer and practical engineering applications (e.g. post-use separation). In this study, a metal -free N-doped reduced graphene oxide (N- rGO) catalyst was prepared via a facile hydrothermal method. N-rGO filters were then synthesized by facile vacuum filtration, such that water can flow through nanochannels within the filters. Various advanced characterization techniques were employed to obtain structural and compositional information of the as-synthesized N-rGO filters. An optimized phenol oxidative flux of 0.036 ± 0.002 mmol-rr¹ was obtained by metal-free catalytic activation of persulfate at an influent persulfate concentration of 1.0 mmo!-L- ¹ and filter weight of 15 mg, while a N-free rGO filter demonstrated negligible phenol oxidation capability under similar conditions. Compared to a conventional batch system, the flow-through design demonstrates obviously enhanced oxidation kinetics (0.036 vs. 0.010 mmol-rr¹), mainly due to the liquid flow through the filter leading to convection-enhanced transfer of the target molecule to the filter active sites. Overall, the results exemplified the advantages of organic compound removal by catalytic activation of persulfate using a metal-free catalyst in flow through mode, and demonstrated the potential of N-rGO filters for practical environmental applications.

[00142] In electronics, Nitrogen-doped graphene sheet exhibits a crossover from p- type to n-type behavior and a strong enhancement of electron-hole transport asymmetry.

[00143] The present invention can be adapted for use in chemical sensors as described in an article titled "Ultrasensitive sensor using N-doped graphene" on PHSY.ORG website in the Nanotechnology / Nanomaterials section dated July 22, 2016. A highly sensitive chemical sensor based on Raman spectroscopy and using nitrogen-doped graphene as a substrate was developed by an international team of researchers working at Penn State. In this case, doping refers to introducing nitrogen atoms into the carbon structure of graphene. This technique can detect trace amounts of molecules in a solution at very low concentrations, some 10,000 times more diluted than can be seen by the naked eye.

[00144] The present invention can be adapted for use in biomedical applications as described in an article titled "Three-dimensional nitrogen-doped graphene as an ultrasensitive electrochemical sensor for the detection of dopamine'¹ authored by Xiaomiao Feng et al. in Nanoscale 2015, 7, 2427-2432, first published online on December 22, 2014. Abstract: Three-dimensional nitrogen-doped graphene (3D N- doped graphene) was prepared through chemical vapor deposition (CVD) by using porous nickel foam as a substrate. As a model, a dopamine biosensor was constructed based on the 3D N -doped graphene porous foam. Electrochemical experiments exhibited that this biosensor had a remarkable detection ability with a wide linear detection range from 3 * 10^~6 M to 1 χ 10^~4 and a low detection limit of 1 nM. Moreover, the fabricated biosensor also showed an excellent anti-interference ability, reproducibility, and stability.

[00145] The present invention can be adapted for use in photocatalytic hydrogen generation as described in an article titled "Nitrogen-Doped Graphene for Photocatalytic Hydrogen Generation" authored by Dong Wook Chang et al. in Chemistry - An Asian Journal, Volume 11 , Issue 8, April 20, 2016, pp 1125-1137, first published online on February 2, 2014. Abstract: Photocatalytic hydrogen (H2) generation in a water splitting process has recently attracted tremendous interest because it allows the direct conversion of clean and unlimited solar energy into the technologically highly attractive energy resource of H2. For efficient photocatalytic H2 generation, the role of the photocatalyst is critical. With increasing demand for more efficient, sustainable, and cost-effective photocatalysts, various types of semiconductor photocatalysts have been intensively developed. In particular, on the basis of its superior catalytic and tunable electronic properties, nitrogen-doped graphene is a potential candidate for a high-performance photocatalyst. Nitrogen- doped graphene also offers additional advantages originating from its unique two- dimensional sp²-hybridized carbon network including a large specific surface area and exceptional charge transport properties. It has been reported that nitrogen-doped graphene can play diverse but positive functions including photo-induced charge acceptor/mediator, light absorber from UV to visible light, n-type semiconductor, and giant molecular photocatalyst. Herein, we summarize the recent progress and general aspects of nitrogen-doped graphene as a photocatalyst for photocatalytic H2 generation. In addition, challenges and future perspectives in this field are also discussed.

[00146] The present invention provides a method of fabricating the nanoparticle incorporated graphene 2D and 3D structures. Si incorporated graphene, Copper incorporated graphene, Gold incorporated graphene are exemplary embodiments of the graphene-nanomaterial incorporated structure as demonstrated in Example 2.

[00147] As shown in Figure 10, the main features in the Raman spectra of Silicon incorporated graphene (SiGr) grown by the precursor of the present invention are the G band and D band, which lie at around 1582-1592 cm ¹ and 1340-1360 cm-¹, respectively. Another characteristic feature in graphene, the 2D band, appears at round 2700 - 2710 cm ¹. Also, the presence of an intense band around 516 cnrr which corresponds to silicon.

[00148] Some advantages of the present invention process are: [00149] Fabrication is easy and inexpensive [00150] Large scale SiGr is possible [00151] No hazardous gases are required [00152] 2D and 3D structures are possible

[00153] Any type of incorporation metal nanoparticle, semiconducting nanoparticle or insulating nanoparticles is achievable

[00154] Some applications for the present invention process are as follows. [00155] Chemical Sensors

[00156] The present invention can be adapted for use in electronics as described in a PhD project description titled "Graphene-Silicon Hybrid Electronics for Defense Applications" supervised by Dr. Haigh and Professor Geim, University of Manchester. Project Description: Conventional silicon based electronics have performance, energy and reliability limitations which can be overcome in the latest generation of graphene- silicon hybrid electronics. However, in defense applications these devices may be subjected to an unusually high level of ion radiation as a result of the exposure to cosmic rays, electromagnetic pulses and nuclear incidents. An understanding of the effect of ion irradiation on graphene based electronics is therefore essential the potential of graphene is to be successfully exploited. In this work, you will investigate the sensitivity of graphene-based electronics to ion-beam irradiation. You will use the Physics clean room facilities to enable you to fabricate and characterise silicon- graphene hybrid devices including performing electronic transport and magnetization measurements. You will then investigate the effect of various ion beam irradiation regimes on the function of these devices. Property measurements will be combined with structural characterisation using scanning electron microscopy and transmission electron microscopy in order to determine the extent of ton penetration. The eventual aim of this project will be to use the knowledge acquired to design new architectures for radiation-hard graphene-silicon hybrid devices that are less susceptible to damage. This project is supported through a grant from the U S Defense Threat Reduction Agency and is likely to involve annual trips to the U.S.

[00157] The present invention can be adapted for use in in fuel cells, supercapacitors, and Li ion batteries as described in an article titled "Three- Dimensional Interconnected Network of Graphene-Wrapped Silicon/Carbon Nanofiber Hybrids for Binder-Free Anodes in Lithium-Ion Batteries" authored by Dr. Ming-Shan Wang et al. in ChemElectroChem, Volume 2, Issue 11 , November 2015, pp 169-1706, first published online on July 6, 2015. Abstract: A three-dimensional (3D) silicon/carbon nanofiber-graphene (Si/CNF-G) nanostructure is constructed by encapsulating Si nanoparticles in carbon nanofibers, followed by wrapping with graphene nanosheets. The graphene-wrapped silicon/carbon nanofibers hybrids have the advantages of good dispersion of Si nanoparticles inside the 3D carbon network. Meanwhile, the 3D carbon network can also act as a current collector to promote charge transfer and maintain stable electrical contact of the Si nanoparticles. The resulting Si/CNF-G composites can be used directly as binder-free electrodes. The composite exhibits a stable capacity retention and a reversible capacity of 878 mAh g^~ for up to 100 cycles, along with a high rate capacity (514 mAh g^~1 at 5.0 A g^_1). These results provide a promising research platform for fabricating stable electrodes with improved electrochemical performance.

[00158] The present invention can be adapted for use in Terahertz Devices as described in an article titled "Active graphene-silicon hybrid diode for terahertz waves" authored by Quan Li et al. in Nature Communications 6, article number 7082 (2015), published on-line on May 1 1 , 2015. Abstract: Controlling the propagation properties of the terahertz waves in graphene holds great promise in enabling novel technologies for the convergence of electronics and photonics. A diode is a fundamental electronic device that allows the passage of current in just one direction based on the polarity of the applied voltage. With simultaneous optical and electrical excitations, we experimentally demonstrate an active diode for the terahertz waves consisting of a graphene-silicon hybrid film. The diode transmits terahertz waves when biased with a positive voltage while attenuates the wave under a low negative voltage, which can be seen as an analogue of an electronic semiconductor diode. Here, we obtain a large transmission modulation of 83% in the graphene-silicon hybrid film, which exhibits tremendous potential for applications in designing broadband terahertz modulators and switchable terahertz plasmonic and metamaterial devices.

[00159] The present invention can be adapted for use in photonic devices as described in a presentation titled "Hybrid graphene-silicon photonics devices" authored by Dries Van Thourhout et al, published in 2015 European Conference on Optical Communication (ECOC), Date of Conference: 27 Sept -1 Oct. 2015, Date Added to IEEE Xplore: 03 December 2015. The presentation reviewed state-of-the-art of hybrid graphene silicon photonics devices, discussing electro-absorption modulators, detectors and controllable saturable absorption.

[00160] The present invention also provides a method of fabricating graphene hybrid 2D and 3D structures like carbon nanotube-graphene, boron nitride nanotube- graphene, semiconductor oxide nanostructures, carbon nanofibers, diamond- graphene hybrid, and their combination. A graphene-carbon nanotube heterostructure and a graphene-semiconductor oxide nanostructure heterostructure such as graphene-Sn02 nanorods graphene-Si nanowires heterostructures are exemplary embodiments of the graphene-nanomaterial heterostructure as demonstrated in Example 3.

[00161] Figures 1 1A1 -1 1A4 show SEM images of a graphene nanostructure coated foam at low and high magnification showing the presence of the carbon nanotubes (CNTs) together with graphene. [00162] As shown in Figure 1 1 B, the main features in the Raman spectra of CNT- graphene (CNT-Gr) grown by the present invention precursor are the G band and D band, which lie at around 1582-1592 cm ¹ and 1340-1360 crrr¹ (due to the presence of CNTs), respectively. Another characteristic feature in graphene, the 2D band, appears at round 2700-2710 cm ^"1.

[00163] Figures 1 1 C1 -1 1 C2 show the EDX spectrum of the image (a) confirming the presence of graphene and Si together in the fabricated material.

[00164] Using the processes and techniques disclosed above, a diamond-graphene hybrid can also be produced. Figures 14A-B are SEM images of diamond-graphene hybrid structure. Figure 14C shows the Raman spectrum of pure diamond paste used to incorporate in graphene structure. The presence of a sharp 1333 cm-¹ band corresponds to sp³-hybridized carbon. Figure 14D shows the Raman spectrum of diamond-graphene hybrid structure. The presence of a minor sharp band near 1342 cm^"1 corresponds to the defect introduced in the graphene structure due to incorporation of diamond G band around 1592 cm-¹ and 2D band for graphene near 2680 cm-¹. Figure 14E shows the Raman spectrum of a diamond-graphene hybrid structure. The presence of a sharp band near 1333 cm-¹ corresponds to the diamond G band around 1590 cm and the 2D band for graphene near 2680 cm-¹.

[00165] Some advantages of the process of the present invention are as follows:

[00166] Fabrication is easy and inexpensive

[00167] Large scale SiGr is possible

[00168] Hazardous gases are not required

[00169] 2D and 3D structures are possible

[00170] Any type of graphene -nanostructure hybrids e.g. nanotubes-graphene, nanowires-graphene, quantum dots-graphene hybrid, nanorod-graphene etc. is achievable

[00171] Some applications for the present invention are as follows: [00172] The present invention can be adapted for use in electrochemical energy storage as described in an article titled "Recent advances in graphene-based hybrid nanostructures for electrochemical energy storage" authored by Pan Xiong et al. in Nanoscale Horizons, 2016, 1 , pp 340-374, published on-line March 16, 2016. Abstract: In recent years, graphene has emerged as a promising candidate for electrochemical energy storage applications due to its large specific surface area, high electrical conductivity, good chemical stability, and strong mechanical flexibility. Moreover, its unique two-dimensional (2D) nanostructure can be used as an ideal building block for controllable functionalization with other active components and the resulting graphene-based hybrids exhibit desirable properties for improved energy storage capability. This review summarizes the most recent progress on graphene and graphene-based hybrid nanostructures for three frontier electrochemical energy storage device applications, i.e. , lithium-ion batteries, lithium-sulfur batteries and supercapacitors. Finally, we outline the future perspectives and trends in this research field including several challenges and opportunities.

[00173] The present invention can be adapted for use in Li ion batteries as described in an article titled "Self-Assembled TiO-Graphene Hybrid Nanostructures for Enhanced Li-Ion Insertion" authored by Donghai Wang et al. in ACS Nano, 2009, 3(4), pp 907-914, published on-line March 26, 2009. Abstract: We used anionic sulfate surfactants to assist the stabilization ofgraphene in aqueous solutions and facilitate the self-assembly of in situ grown nanocrystalline TiO, rutiie and anatase, with graphene. These nanostructured Ti02- graphene hybrid materials were used for investigation of Li-ion insertion properties. The hybrid materials showed significantly enhanced Li-ion insertion/extraction in Ti02. The specific capacity was more than doubled at high charge rates, as compared with the pure Ti02 phase. The improved capacity at high charge— discharge rate may be attributed to increased electrode conductivity in the presence of a percolated graphene network embedded into the metal oxide electrodes.

[00174] The present invention can be adapted for use in supercapacitors as described in an article titled "Graphene/Carbon Nanotubes Hybrid Electrode Material for High Performance Supercapacitor" authored by Yongzhen Wang et al. in Nano, July 2015, Vol. 10, No. 05, published on-line May 19, 2015. Abstract: A graphene (GN)/carbon nanotubes (CNTs) nanocomposite electrode material were prepared via reduction of exfoliated graphite oxides in the presence of CNTs pretreated by mixed acid. The GN/CNTs nanocomposite characterized by X-ray diffraction (XRD), Raman spectrum (Raman) and scanning electron microscope (SEM) has a layered structure with CNTs uniformly sandwiched between the GN sheets, which efficiently decreased the agglomeration GN sheets. Electrochemical data demonstrate that the GN/CNT exhibited higher specific capacitance than that of graphene.

[00175] Yet another embodiment provides a method of fabricating Nitrogen doped Copper incorporated graphene (NCuGr) as demonstrated in Example 4.

[00176] As shown in Figure 7G2A, the main features in the Raman spectra of Nitrogen doped Copper incorporated graphene (NCuGr) grown by the present invention precursor are the G band and D band, which lie at around 1582 cm - 592 cm^-1 and 1340 - 1360 cm ¹, respectively. Another characteristic feature in graphene, the 2D band, appears at round 2700-2710 cm-¹.

[00177] In case of NCuGr, D band is of higher intensity due to the presence of defects (as a result of Copper incorporation) and the G band is a little asymmetrical.

[00178] Experimentally, the 2D band can be used to determine the number of graphene layers. Figure 7G2B shows the deconvo!ution of 2D band of the Raman spectrum shown in Figure 7G2A using peak fit software. It was found that the experimental curve (dashed line) in the range from 2600 cm ¹- 2800 cm ¹ is coinciding with the fitted curve (solid line) showing four elemental peaks, as predicted by the double resonance Raman model, can be distinguished in the Raman spectrum of bilayer graphene.

[00179] Figures 7G1A-B show SEM images of NCuGr showing the morphology of the film at low magnification and at higher magnification.

[00180] Figures 7G3A-E shows the color EDX of the image a showing the presence of Nickel (substrate), carbon (graphene). Copper (nanoparticles incorporated) and the Nitrogen (doping material). The Nitrogen signals are less as the time of acquisition of data is less.

[00181] Some advantages of the process of the present invention are as follows. [00182] Fabrication is easy and inexpensive

[00183] Large scale NCuGr is possible [00184] No hazardous gases are required [00185] 2D and 3D structures are possible

[00186] Any type of doped n type, p type graphene together with incorporation (nanoparticles, nanotubes, nanowires-, quantum dots, nanorods etc.) is achievable

[00187] Some applications of the present invention are as follows.

[00188] The present invention can be adapted for use in electronics as described in an article titled "Nitrogen-Doped Activated Carbon-Based Ammonia Sensors: Effect of Specific Surface Functional Groups on Carbon Electronic Properties" authored by Nikolina A. Travlou et al. in ACS Sensors, 2016, 1 (5), pp 591-599, published on-line March 18, 2016. Abstract: Wood-based commercial activated carbon (BAX) and its oxidized counterpart (BAX-O) were treated with melamine and then heated at 450 °C in nitrogen. Further oxidation with nitric acid was also applied. The carbons were tested for ammonia sensing (45-500 ppm of Nhta). Even though all samples exhibit p- type conduction, their exposure to NHs led to different electrical outcomes. It was found that the electronic and transport properties of the carbons strongly depend on the type of nitrogen groups/surface defects, their concentration, and distribution in the carbon matrix. Pyridines and nitropyridines are the most important. A competition between the structural and chemical features of the carbons as those governing the sensing signals was observed. Exposure to ammonia altered the surface chemistry of the samples, and therefore their electrical properties. When sensitivity to H2S was tested to evaluate the selectivity of our sensors, the results showed that the chips are selective to NH3 in terms of the response time and magnitude of the signal changes.

[00189] The present invention can be adapted for use in supercapacitors as described in an article titled "Flexible free-standing 3D porous N-doped graphene- carbon nanotube hybrid paper for high-performance supercapacitors" authored by Wei Fan et al. in RSC Advances, 2015, 5, 9228-9236, published on-line January 2, 2015. Abstract: The nanoarchitecture of carbon with assembled building blocks on diverse scales is of great importance for energy storage. Herein, we demonstrate high- performance supercapacitors by building a three-dimensional (3D) porous structure that consists of a N-doped graphene-carbon nanotube (CNT) hybrid. The 3D porous nitrogen-doped graphene-CNT (p-N-GC) hybrid paper was fabricated by using polystyrene (PS) colloidal particles as a sacrificial template, followed by calcination to remove PS to generate macropores, to reduce graphene oxide (GO) into graphene, and to realize N-doping simultaneously by one step. The as-prepared p-N-GC paper with high porosity, conductivity and flexibility has a high specific capacitance of 294 F g^_1 at a current density of 1 A g^~1 in 6 M KOH electrolyte solution, as well as good rate capability and cycle stability. The greatly enhanced electrochemical performance can be ascribed to the synergistic effect of the 3D porous nanostructure, effective CNT intercalation, and nitrogen-doping, suggesting that p-N-GC as novel electrode materials may have potential applications in high-performance energy storage devices.

[00190] Examples:

[00191] Figure 12 shows a test specimen that is a 1 inch by 1 inch copper foil substrate with 4 mg of semisolid precursor. The specimens move through the test chamber at a rate of I inch per minute. Test specimens labeled CGS-34, CGS-37, CGS-40 were exposed to Nitrogen gas flowing at or about 5 seem to keep the pressure stable. Nitrogen gas is not flowing during CGS-41. All specimens show graphene on the copper substrates. Results of the tests are illustrated in Figures 13A-13R. The graphene growth occurred between 15 and 22 minutes (about a 7-minute dwell duration) with test chamber air temperatures ranging from 800 °C.to 1000 °C.

[00192] Figures 15A-B illustrate another embodiment of the present invention where hydrocarbon gasses are passed over a graphene sheet to form 3D nanostructures.

[00193] Figure 15A illustrates a drop of precursor melt (e.g. petroleum Jelly, petrolatum) containing metal nanoparticles (e.g. gold, Iron, copper) as discussed above being deposited of a substrate (e.g., a copper foil) to form a melt coated substrate. The metal nanoparticles may be patterned in the coating, e.g., using photolithography or screen printing or spray coating. The melt coated substrate is subjected to CVD in an inert atmosphere to a temperature in the range of 450-1000°C for a predetermined time ranging from 10 seconds to 45 minute to form a graphene sheet, and then allowing nanostructure forming precursor gasses (e.g. methane, silane, borazine) to flow for 1 to 30 minutes to form nanostructures on the graphene sheet.

[00194] Figure 15B illustrates a precursor and nanoparticles being applied to a substrate to form a coated substrate. The coated substrate is subjected to CVD in an inert atmosphere to a graphene growth temperature in the range of 450-1000°C for a predetermined time ranging from 10 seconds to 45 minute to form a graphene sheet, and then allowing nanostructure forming precursor gasses (e.g. methane, silane, borazine) to flow for 1 to 30 minutes at the same pressure to form nanostructures on the graphene sheet. The metal nanoparticle present in the graphene structure will behave as a catalyst to grow nanotubes or nanowires of, from example, silicon or carbon.

[00195] Figures 16A-D show illustrations of embodiments of continuous manufacturing process systems for a variety of applications.

[00196] Figure 16A is an illustration of a continuous catalyst substrate 1602 on an unwind roll 1604 fixedly positioned at one end of the stationary surface 1606. The continuous catalyst substrate 1602 will be connected to a wind roll 1608 fixedly position at an opposing end of the stationary surface 1606. Disposed on the stationary surface 1606 between the unwind roll 1604 and the wind roll 1608 are the multi-precursor dispenser 1610, an energy device 1612, and a cooling device 1614. An alternative to the reel-to-reel catalyst substrate is a conveyor belt 702 illustrated in Figure 17A, where the conveyor belt 1702 is pre-treated or cleaned 1701 prior to dispensing the precursor from the precursor dispenser 1706 on to the continuous catalyst substrate to remove any residue and/or contaminants caused by the environment and/or previous graphene fabrication thereon and graphene removal steps therefrom. The conveyor belt can be made in part or whole of a catalyst material depending on the catalyst's mechanical properties to sustain thermal and mechanical stresses. When the conveyor belt is made in part with a catalyst material, then the other materials of the conveyor belt can be conventional materials utilized in commercially available conveyor belts and compatible to be joined with the catalyst material.

[00197] The multi-precursor dispenser 1610 can dispense as many precursors as required for the desire end-product on to the continuous catalyst substrate 1602 from one precursor (Precursor 1 (P1 )) to an infinite number of precursors (Precursor n (Pn)), where "n" refers to any number up to infinity). Also, illustrated on Figure 16A are Precursor 2 (P2) and Precursor 3 (P3). The precursor dispenser 1610 can dispense the precursor into a pattern from straight lines (P1 , P2-2, P3) to curved lines (P2-1 ).

[00198] The precursors can be doped, undoped, or incorporated with nanoparticles. Any commercially available process of preparing the precursor with nanoparticles is acceptable including, for not limited to, pre-mixing the nanoparticles with the precursor prior to adding the precursor to the precursor dispenser 1610, or providing another embodiment (not shown) of the precursor dispenser 1610 with a separate nanoparticle dispenser therein that dispenses nanoparticles on the top surface of the dispensed precursor on the catalyst substrate, thereby eliminating the need of pre-mixing the nanoparticles with the precursor in advance of adding the precursor to the precursor dispenser 1610.

[00199] The energy device 1612 can be any commercially available energy device (e.g. , oven, heating filament, coil, furnace, flash heating, plasma, radiant, acoustic, electromagnetic) capable of heating the precursor(s) to a predetermined temperature(s) and/or heating rate, as discussed in detail above, to facilitate or activate the growth of graphene of the particular precursor. The energy device can have heating zones to provide the predetermined temperature for a predetermined time for a particular precursor and possibly isolate or insulate the other precursors and previously thermally activated precursor from further exposure to the immediately applied predetermined heating temperature. The cooling device 1614 can be any commercially available refrigeration system that can be set for a predetermined accelerated cool down rate of the activated precursor to a predetermined cooling temperature to form graphene from a particular precursor, for example, graphene G2 from Precursor 2 (P2-1 ). The cooling device 1614 can have multiple cooling zones therein to provide the predetermined temperature and/or cool down rate for a particular precursor and possibly isolate or insulate the other activated precursors and grown graphene from further exposure to the immediately applied predetermined cooling temperature. Alternatively, the cooling device 1614 can be set for a non-assisted or natural cool down at ambient temperature.

[00200] Figure 16B is an illustration of a plurality of substrates 1626, for example catalyst foil, and a continuous conveyor belt 1628 instead of the continuous catalyst substrate 1602 discussed above in Figure 16A. Other components and equipment disclosed with respect to Figure 16A are the same in Figure 16B and are repeated below for the reader's convenience. Disposed on the stationary surface 1606 are the multi-precursor dispenser 1610, an energy device 1612, and a cooling device 1614. The multi-precursor dispenser 1610 can dispense as many precursors as required for the desire end-product on to the plurality of substrates 1626 from one precursor (Precursor 1 (P1 )) to an infinite number of precursors (Precursor n (Pn)), where "n" refers to any number up to infinity). Also, illustrated on Figure 16B are Precursor 2 (P2) and Precursor 3 (P3). The precursor dispenser 1610 can dispense the precursor into a pattern from straight lines (P1 , P2-2, P3) to curved lines (P2-1 ).

[00201] The precursors can be doped, undoped, or incorporated with nanoparticles. Any commercially available process of preparing the precursor with nanoparticles is acceptable including, for not limited to, pre-mixing the nanoparticles with the precursor prior to adding the precursor to the precursor dispenser 1610, or providing another embodiment (not shown) of the precursor dispenser 1610 with a separate nanoparticle dispenser therein that dispenses nanoparticles on the top surface of the dispensed precursor on the catalyst substrate, thereby eliminating the need of pre-mixing the nanoparticles with the precursor in advance of adding the precursor to the precursor dispenser 1610.

[00202] The energy device 1612 can be any commercially available energy device (e.g., oven, heating filament, coil, furnace, flash heating, plasma) capable of heating the precursor(s) to a predetermined temperature(s), as discussed in detail above, to facilitate or activate the growth of graphene of the particular precursor. The energy device can have heating zones to provide the predetermined temperature for a predetermined time for a particular precursor and possibly isolate or insulate the other precursors and previously thermally exposed precursor from exposure to the immediately applied predetermined heating temperature. The cooling device 1614 can be any commercially available refrigeration system that can be set for a predetermined accelerated cool down rate of the activated precursor to a predetermined cooling temperature to form graphene from a particular precursor, for example, graphene G2 from Precursor 2 (P2-1). The cooling device can have multiple cooling zones therein to provide the predetermined temperature and/or cool down rate for a particular precursor and possibly isolate or insulate the other activated precursors and previously grown graphene from further exposure to the immediately applied predetermined cooling temperature. Alternatively, the cooling device 1614 can be set for a non-assisted or natural cool down at ambient temperature.

[00203] The continuous graphene processing systems disclosed in Figures 16C and 16D are similar to the systems disclosed in Figures 16A and 16B, respectfully. The difference is the process to dispense the precursor. In Figures 16A and 16B, the precursors are dispensed from a single multi-precursor dispenser 1610. Whereas in Figures 16C and 16D, the precursors are singularly dispensed from a plurality of single precursor dispensers. The energy device and cooling device can immediately follow the single precursor dispensing operation. The arrangement of single precursor dispenser (1650A... n), energy device (1652A... n), and cooling device (1654A... n) allows for the heating and cooling rates, and predetermined temperatures to be targeted for the particular precursor characteristics to optimize graphene growth and the graphene's properties.

[00204] The graphene growth process is similar relative to Figures 16C and 16D with the difference being the catalyst substrate transportation systems: Figure 16C illustrates a continuous catalyst substrate 1602 and Figure 16D illustrates a plurality of substrates 1626, for example catalyst foil, and a continuous conveyor belt 1628. Below is the process applicable to both transportation systems:

[00205] A. Providing a catalyst substrate transportation system (1602, 1628), a catalyst substrate (1602 catalyst incorporated into a roll in a reel-to-reel system, 1626), two or more precursor dispensers (1650A... n), two or more energy devices energy device (1652A... n), and two or more cooling devices (1654A... n); [00206] B. Advancing the catalyst substrate transportation system (1602, 1628) to convey the catalyst substrate (1602, 1626) through a first precursor dispenser (1650A) of the two or more precursor dispensers (1650A... n);

[00207] C. Dispensing a first precursor (P1) in a predetermined pattern (3 straight perpendicularly arranged lines) from the first precursor dispenser (1650A) of the two or more precursor dispensers (1650A... n) on to the catalyst substrate (1602, 1626);

[00208] D, Advancing the catalyst substrate transportation system (1602, 1628) to convey the catalyst substrate (1602, 1626) with the first patterned precursor (P1 ) through a first energy device (1652A) of the two or more energy devices (1652A... n);

[00209] E. Triggering the first energy device (1652A) of the two or more energy devices (1652A... n) to a first predetermined heating temperature for a first predetermined heating time interval to activate the first patterned precursor (P1 ) on the catalyst substrate (1602, 1626), see the disclosure in previous sections of this application for examples of heating temperatures and time intervals;

[00210] F. Advancing the catalyst substrate transportation system (1602, 1628) to convey the catalyst substrate (1602, 1626) with the first activated precursor (P1) through a first cooling device (1654 A) of the two or more cooling devices (1654A... n);

[00211] G. Triggering the first cooling device (1654A) of the two or more cooling devices (1654A... n) to a first cooling temperature for a first predetermined cooling time interval to form a first graphene pattern (G1) from the first activated precursor (P1) on the catalyst substrate (1602, 1626), see the disclosure in previous sections of this application for examples of cooling temperatures and time intervals; and

[00212] H. Advancing the catalyst substrate transportation system (1602, 1628) to convey the catalyst substrate (1602, 1626) with the first graphene pattern (G1) through one or more subsequent precursor dispensers (1650B) of the two or more precursor dispensers (1650A... n), one or more subsequent energy devices (1652B) of the two or more energy devices (1652A... n), and one or more subsequent cooling devices (1654B) of the two or more cooling devices (1654A... n), and repeating the above steps to form two or more graphene patterns, some in proximity of the first graphene pattern (G1) - for example graphene (G2, G3) formed from Precursors 2 (P2) and 3 (P3),

[00213] The precursors in the single precursor dispensers can be different or the same in the series of single precursor dispensers or in the subsequent precursor dispenser. The precursors can be doped, undoped, or incorporated with nanoparticles. Any commercially available process of preparing the precursor with nanoparticles is acceptable including, for not limited to, pre-mixing the nanoparticles with the precursor prior to adding the precursor to the precursor dispenser (1650A..n), or providing another embodiment (not shown) of the precursor dispenser (1650A..n) with a single nanoparticle dispenser therein that dispenses nanoparticles on the top surface of the dispensed precursor on the catalyst substrate, thereby eliminating the need of pre- mixing the nanoparticles with the precursor in advance of adding the precursor to the precursor dispenser 1610.

[00214] The heating temperatures, heating time intervals, and heating rates to activate precursor(s) on the catalyst substrate can be different or the same in the series of energy devices or in the subsequent energy device.

[00215] The cooling temperatures, cooling time intervals, and cooling rates to form a graphene pattern can be different or the same in the series of cooling devices or in the subsequent cooling device.

[00216] However, one of ordinary skill in the art will realize that there are many alternative embodiments with many possible combinations and arrangements for the disclosed inventions. For example, one alternative embodiment can include a series of single precursor dispensers instead of a multi-precursor dispenser being arranged or oriented or ordered before the energy device and cooling device for an equivalent process illustrated in Figures 16A and 16B

[00217] Continuous processing disclosed with respect to Figures 16A-D can be accomplished in various ways. The substrates 1602, 1626 can travel along the stationary surface 1606 at a constant rate or an incremental rate, which can include (but not required) starting-and-stopping of the roll or conveyor for dispensing precursor or to satisfy temperature dwell time requirements for heating and/or cooling purposes. Some embodiments of the catalyst substrate transportation system are capable of controlling the advancement rate from a constant rate through one device to an incremental rate (including fully stopped) through the other device in the same embodiment. The catalyst substrate transportation system can perform similar to a pseudo-batch process, for example, by dispensing the precursor for the next graphene pattern contemporaneous with the end of the cooling cycle of the predecessor graphene pattern. The length of the energy device can range from a small size, for example flash heating, to achieve precursor melting/activation temperature for graphene growth activation, to a long size with plurality of temperature zones to simulate temperature ramp or a plurality of activation temperatures for various precursors. The length of the cooling device can also vary in size to achieve desired results of graphene growth. Cooling device can be ambient or temperature controlled for accelerated cooling rate.

[00218] Figure 17A is a schematic view illustrating a graphene growth and transferring apparatus 1700B according to an embodiment of the present invention. Figures 17B-D are cross-sectional views illustrating an operation in which graphene is transferred from a continuous catalyst substrate 1702 to transfer strips 1704A, 1704B in the graphene transferring apparatus illustrated in Figure 17A of the present invention. One embodiment of the continuous catalyst substrate 1702 can be a conveyor belt where the surfaces 1702A, 1702B of the continuous catalyst substrate 1702 are pre-treated or cleaned 1701 prior to dispensing the precursor from the precursor dispenser 1706 on to the continuous catalyst substrate 1702 to remove any residue and/or contaminants caused by the environment and/or previous graphene fabrication thereon and graphene removal steps therefrom.

[00219] The precursors can be doped, undoped, or incorporated with nanoparticles. Any commerciaily available process of preparing the precursor with nanoparticles is acceptable including, for not limited to, pre-mixing the nanoparticles with the precursor prior to adding the precursor to the precursor dispenser 1706, or providing another embodiment (not shown) of the precursor dispenser 1706 with a single nanoparticle dispenser therein that dispenses nanoparticles on the top surface of the dispensed precursor on the catalyst substrate, thereby eliminating the need of pre-mixing the nanoparticles with the precursor in advance of adding the precursor to the precursor dispenser 1706. [00220] The conveyor belt can be made in part or whole of a catalyst material depending on the catalyst's mechanical properties to sustain thermal and mechanical stresses. When the conveyor belt is made in part with a catalyst material, then the other materials of the conveyor belt can be conventional materials utilized in commercially available conveyor belts and compatible to be joined with the catalyst material. An alternative to the conveyor belt 1702 is reel-to-reel catalyst substrate (continuous catalyst substrate 1602, the unwind roll 1604, the wind roll 608) illustrated in Figure 16A, shown as a dashed line in Figure 17A,

[00221] In the graphene growth operation, graphene 1714A, 1714B is formed on one or two surfaces 1702A, 1702B, respectfully, of a continuous catalyst substrate 1702 by using techniques and processes described in this specification. Catalyst substrates used in forming the graphene 1714A, 1714B may include materials including, but not limited to, at least some selected from the group consisting of nickel (Ni), cobalt (Co), iron (Fe), platinum (Pt), gold (Au), aluminum (Al), sapphire (AI2O3), chromium (Cr), copper (Cu), germanium (Ga), gallium arsenide (GaAs), gallium nitride (GaN), magnesium (Mg), manganese (Mn), rhodium (Rh), silicon (Si), tantalum (Ta), titanium (Ti), tungsten (W), uranium (U), vanadium (V), zirconium (Zr), mica and stainless steel foam. However, the catalyst substrate is not limited thereto, and may include other elements than those described above. By conveying the continuous catalyst substrate 1702 into an energy device 1708 together with a precursor 1716A, 1716B disposed on one or two surfaces 1702A, 1702B of the continuous catalyst substrate 1702 by a precursor dispenser 1706 and heating or energizing the same at a graphene activation temperature, and then conveying the activated precursor 1711A, 1711 B to the cooling device 1709, whereby the graphene 1714A, 1714B is formed on the one or two surfaces 1702A, 1702B, respectively, of continuous catalyst substrate 1702. The graphene 1714A, 1714B may be formed as a single layer. Other embodiments of the present invention may generate multiple graphene layers.

[00222] Referring to Figure 17A-D, the apparatus and components to transfer or separate graphene from the continuous catalyst substrate 1702 includes a first unwinding reel 171 OA, a second unwinding reel 1710B, a first roller 1710C, a second roller 1710D, a third roller 1710E, a fourth roller 171 OF, a first winding reel 1710G, and a second winding reel 1710H. Transfer strips 1704A, 1704B having an adhesive first surface 1704C, 1704D are wound around the first unwinding reel 171 OA and the second unwinding reel 1710B; the first and second unwinding reels 171 OA, 1710B unwind the transfer strips 1704A, 1704B onto each of the two surfaces 1702A, 1702B of the continuous catalyst substrate 1702.

[00223] Referring to Figure 17A, adhesive barriers 1716A, 1716B are attached on the adhesive first surfaces 1704C, 1704D in advance. Adhesive barriers 1716A, 1716B are not adhesive and thus may prevent the transfer strips 1704A, 1704B from sticking and prevent penetration of foreign substances into the transfer strips 1704A, 1704B. The adhesive barriers 1716A, 1716B are taken off from the transfer strips 1704A, 1704B using adhesive barrier collecting rollers 1718A, 1718B before the transfer strips 1704A, 704B are put between the first and second rollers 1710C, 1710D.

[00224] As noted above, the transfer strips 1704A, 1704B are disposed on the first and second surfaces 1702A, 1702B of the continuous catalyst substrate 1702 to which the graphene 1714A, 1714B are formed. The continuous catalyst substrate 1702 and the transfer strips 1704A, 1704B are put between the first through fourth rollers 1710C, 1710D, 1710D, 1710E so as to compress the graphene 1714A, 1714B of the continuous catalyst substrate 1702 and the transfer strips 1704A, 1704B. The transfer strips 1704A, 1704B are disposed such that the adhesive first surfaces 1704C, 1704D contacts the graphene 1714A, 1714B. The continuous catalyst substrate 1702 and the transfer strips 1704A, 1704B, which are compressed against each other primarily by being passed between the first and second rollers 1710C, 1710D, are further rigidly compressed against each other by being passed between the third and fourth rollers 1710E, 1710F. The continuous catalyst substrate 1702 and the transfer strips 1704A, 1704B, which are separated as illustrated in Figure 17B, are indirectly adhered to each other through this operation while having the graphene 1714A, 1714B interposed therebetween as illustrated in FIG. 7C.

[00225] The first and second rollers 1710C, 1710D are symmetrically disposed with respect to a transfer path D1 of the continuous catalyst substrate 1702 and are spaced apart from each other by a predetermined distance. The first roller 1710C and the second roller 1710D press the transfer strips 1704A, 1704B that is unwound from the first unwinding reel 1710A and the second unwinding reel 1710B toward each of the surfaces 1702A, 1702B of the continuous catalyst substrate 1702 so as to adhere the adhesive first surfaces 1704C, 1704D of the transfer strips 1704A, 704B to the graphene 1714A, 1714B formed on the surfaces 1702A, 1702B. In addition to compressing the transfer strips 1704A, 1704B, the first roller 1710C and the second roller 1710D may transport the continuous catalyst substrate 1702 along the transfer path D1.

[00226] Though the above embodiment discloses compression as the technique affix, adhere, bond, join or otherwise bring the transfer strips 1704A, 1704B together with graphene 1714A, 1714B, respectively, one of skill in the art understands that there are other suitable techniques. For example, energy, electro-static, van der waals forces, and cooling can also be used.

[00227] The third and fourth rollers 1710E, 1710F are also symmetrically disposed with respect to a transfer path D1 of the continuous catalyst substrate 1702 and are spaced apart from each other by a predetermined distance. The third and fourth rollers 1710E, 171 OF press the combination of transfer strips 1704A, 1704B, graphene 1714A, 1714B, and continuous catalyst substrate 1702 to further increase the adhesive force between the graphene 1714A, 1714B and the transfer strips 1704A, 1704B. The adhesive force between the transfer strips 1704A, 1704B and the graphene 1714A, 1714B is now greater than the adhesive force between the continuous catalyst substrate 1702 and the graphene 1714A, 1714B, and thus by separating the transfer strips 1704A, 1704B from the continuous catalyst substrate 1702, the graphene 1714A, 1714B are separated from the continuous catalyst substrate 1702 together with the transfer strips 1704A, 1704B as illustrated in Figure 17D.

[00228] The first and second winding reels 1710G, 1710H separates the transfer strips 1704A, 1704B and graphene 1714A, 1714B from the continuous catalyst substrate 1702 as they wind. First and second winding reel 1710G, 1710H are positioned at a perpendicular distance P away from the continuous catalyst substrate 1702 creating a separation angle a with guide rollers 1720A, 1720B, whereby the transfer strips 1704A, 1704B are drawn away from the continuous catalyst substrate 1702 when the transfer strips 1704A, 170 B are wound on to first and second winding reels 1710G, 1710H, respectively. Any angle a greater than zero can be sufficient to break the adhesive bond between the continuous catalyst substrate 1702 and the graphene 1714A, 1714B as the transfer strips 1704A, 1704B are wound on to first and second winding reels 1710G, 1710H, respectively. Since the second surfaces 1704E, 1704F opposite to the first adhesive surface 1704C, 1704D of the transfer strips 1704A, 1704B are not adhesive, even when the transfer strips 1704A, 1704B are wound around the first and second winding reels 1710G, 1710H, parts of the transfer strips 1704 A, 1704B do not stick to each other, and thus the graphene 1714A, 1714B may stably stay adhered to the transfer strips 1704A, 1704B.

[00229] Through the above-described operation, the transfer strips 1704A, 1704B to which the graphene 1714A, 1714B are transferred may be used in the manufacture of substrates of various electronic products by undergoing operations such as a patterning process. Figures 16A-B illustrate non-limiting various patterns indicated as deposited precursors P1 , P2, P3 that formed graphene G1 , G2, G3, respectively.

[00230] According to the graphene growth and transferring method of the current embodiment of the present invention, no etching is required, and the graphene 1714A, 1714B may be directly transferred to the transfer strips 1704A, 1704B from the continuous catalyst substrate 1702 without using a thermal release tape. Thus, the operation of transferring the graphene 1714A, 1714B may be further simplified and the speed of the operation may be increased. In addition, during the etching operation or when attaching or detaching the graphene 1714A, 1714B to and from the thermal release tape, damage to the graphene 1714A, 1714B may be prevented. As a result, damage to the graphene 1714A, 1714B may be effectively prevented in the operation of transferring the graphene 1714A, 1714B.

[00231] In summary, according to the method of growing and transferring the graphene of the current embodiment of the present invention:

[00232] A. Graphene 1714A, 1714B are formed on the two surfaces 1702A, 1702B of the continuous catalyst substrate 1702,

[00233] B. Continuous catalyst substrate 1702 and the graphene 1714A, 1714B are adhered to two transfer strips 1704A, 1704B at the same time, and

[00234] C. Continuous catalyst substrate 1701 is separated from the graphene 1714A, 1714B and the two transfer strips 1704A, 1704B at the same time.

[00235] Thus, the speed of the graphene transferring operation is high.

[00236] In alternative embodiments of the continuous process system, graphene may be separated from the substrate by application of energy at or about the desired locus (such as at the interface between graphene and substrate or proximity of the interface) for separating graphene and substrate and then separately handling each material feed. For example, an energy source can be added upstream or downstream in proximity of third and fourth rollers 1710E, 1710F of Figure 17 to facilitate the separation of the graphene from the substrate by breaking the bond between the substrate 1702 and graphene 1714A, 1714B by way of heat, stimulation, or other means. When the energy source is downstream of the third and fourth rollers 1710E, 1710F, then the energy source can be disposed between the third and fourth rollers 1710E, 1710F and the guide rollers 1720A, 1720B. The energy source could heating, cooling, and other excitation of the substrate, graphene, and/or transfer strip. Another embodiment of the continuous process system is illustrated in Figure 17E and discussed in the detail below.

[00237] Supplying energy, from the energy source, to or in proximity of the substrate and the one or more graphene patterns can induce separation between the substrate and the one or more graphene patterns further comprises heating either the substrate or the one or more graphene patterns using, for example, a laser frequency depending on which material (either the substrate or the one or more graphene patterns) more readily absorbs the laser frequency. Another embodiment of the energy source can focus its energy (e.g., (heating/cooling) at an interface between the substrate, the one or more graphene patterns, or the transfer strip (if present). While another embodiment of the energy source can focus or direct the energy to each component - the substrate, the one or more graphene patterns, and the transfer strip (if present).

[00238] Referring to Figure 17E, the apparatus and components to transfer or separate graphene 1714A from the continuous catalyst substrate 1702 is illustrated. Figures 16A-B illustrate non-limiting various patterns indicated as deposited precursors P1 , P2, P3 that formed graphene G1 , G2, G3, respectively. A varying angle β is formed between the graphene 1714A and continuous catalyst substrate 1702 starting at point X, which as coincident with the center of conveyor roller 1724. Graphene 1714A can be sufficiently rigid such that the bond between continuous catalyst substrate 1702 and graphene 1714A is broken when angle β reaches a predetermined separation angle. Therefore, there will be no need for external sources, such as heat or energy stimulation, to act upon the bonded graphene 1714A and substrate 1702 for separation of the graphene 1714A and continuous catalyst substrate 1702 to occur. In cases where an external source is needed for separation of the graphene 1714A and continuous catalyst substrate 1702 to occur, an energy source 1722 can be added upstream in proximity of conveyor roller 1724 to facilitate the separation of the graphene 1714A from the continuous catalyst substrate 1702 by breaking the bond between the continuous catalyst substrate 1702 and graphene 1714A by way of heat, stimulation or other means.

[00239] Guide rollers 1726A, 1726B can be positioned adjacent conveyor roller 1724 to receive graphene 714A as it exits system 1700E. Guide rollers 1726A, 1726B can be powered to rotate in the direction of the arrows to assist in the movement of graphene 1714A in direction D. Alternatively, guide rollers 1726A ,1726B can be free to rotate without direct power thereto where graphene 1714A is propelled in direction D by the movement of continuous catalyst substrate 1702 as part of conveyor of system 1700E.

[00240] According to the graphene growth and transferring method of the alternative embodiment of the present invention, no etching is required, and the graphene 1714A may be directly transferred without the need of the transfer strip 1704A. Thus, the operation of transferring the graphene 1714A may be further simplified and the speed of the operation may be increased. As a result, damage to the graphene 1714A may be effectively prevented in the operation of transferring the graphene 1714A.

[00241] In summary, according to the method of growing and transferring the graphene of system 1700E of the present invention: [00242] A. Conveyor belt (continuous catalyst substrate) 1702 is pre-treated or cleaned 1701 prior to dispensing the precursor 1716A from the precursor dispenser 1706 on to the continuous catalyst substrate 1702 to remove any residue and/or contaminants caused by the environment and/or previous graphene fabrication thereon and graphene removal steps therefrom;

[00243] B. Conveying the continuous catalyst substrate 1702 into a precursor dispenser 1706 and dispensing a precursor 1716A on to surface 1702A of the continuous catalyst substrate 1702;

[00244] C. Conveying the continuous catalyst substrate 1702 with the dispensed precursor 1716A disposed on surface 1702A into an energy device 1708 and heating or energizing the same at a graphene activation temperature;

[00245] D Conveying the activated precursor 171 1A to the cooling device 1709, whereby the graphene 1714A is formed on surface 1702A of continuous catalyst substrate 1702. The graphene 1714A may be formed as a single layer.

[00246] E. Conveying (optionally) the continuous catalyst substrate 1702 with graphene 1714A to a second energy source to initiate the debonding of graphene 1714A from the continuous catalyst substrate 1702;

[00247] F. Conveying the continuous catalyst substrate 1702 with graphene 1714A to and beyond a predetermined graphene separation point (e.g., X) coincident with varying angle β being greater than zero, and the continuous catalyst substrate 1702 being redirected away from direction D, wherein graphene 1714A separates from continuous catalyst substrate 1702; and

[00248] G. Conveying separated graphene 1714A in direction D for further processing. Separated graphene 1714A can be received by guide rollers 1726A and/or 1726B for stability and retention.

[00249] Thus, the speed of the graphene transferring operation is high.

[00250] The above embodiments illustrated in Figures 16A-17D disclose catalyst substrates. However, in cases where the substrate is made of a non-catalyst material, the catalyst is applied to the non-catalyst substrate

[00251] Now turning to Figure 18 to illustrate another embodiment of the present invention that is a concept for low-cost, low-overhead growth of a graphene layer on extruded iron, steel alloys, and other metals or materials susceptible to corrosion or defects due to exposure to environmental elements. For example, iron and steel alloys that exhibit formation of oxides (rust and scale, FeaCb and FesC FeO, hydrated iron oxides, and iron oxide-hydroxides) are often treated with a coating of oil or grease to minimize corrosion during shipment or storage. This coating can be bothersome to remove and is a potential pollutant. The process conditions of the present invention for the continuous growth of graphene films on metallic surfaces are in the range of temperatures nominally seen by these materials when they emerge from an extrusion die.

[00252] In Figure 18, extrusion die 1800 includes container 1802 having a billet zone 1803 sized to receive billet 1808, a precursor dispenser 1814 adjacent to the billet zone 1803 to dispense a precursor onto the extruded part 1804 while the extruded part 1804 is still at or about graphene formation temperature, and a graphene formation zone 1816 adjacent to the precursor dispenser 1814 to grow graphene 1818 from the precursor on the extruded part 1804 while the extruded part 1804 is still at or about graphene formation temperature. Exit area 1812 is a sealed exit sized to receive the extruded part with graphene without allowing external gas penetration into the controlled environment 1822 during the steps of dispensing at least one precursor from the precursor dispenser onto the extruded part and advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time for graphene growth on the extruded part. The controlled environment will not contain concentrations of oxygen that will react with hot extruded part to cause oxidation within the precursor dispenser 1814 and graphene formation zone 1816 such that with the proper carbon precursor present, graphene 1818 growth on the surface of the extruded part 1804 occurs without additional energy being supplied to grow the graphene from the dispensed precursor. A non-reactant cover gas can be added at cover gas inlet 1820 to the controlled environment at or about 1 atmosphere. The heat generated during the extrusion process is retained by the extruded part 1804 and is sufficient for the growth of graphene onto the extruded part 1804. The graphene 1818 is durable and serves as a rust inhibitor. In addition, graphene 1818 does not need to be removed to further process the extruded part 1804. The graphene 1818 can be painted, welded, machined or bent with no consequences. Also shown in Figure 18 are conventional extrusion tools including ram 1806 that exerts pressure onto pressure pad 1801 , which pushes billet 1808 in direction D toward die 1810 to draw billet 1808 through die 1810 to form extruded part 1804. The size, volumes, and lengths of the precursor dispenser 1814 and graphene formation zone are dependent on the type of materials, rate of advancement of the billet in Direction D, temperature dwell time requirements, and other manufacturing variables that can be determined by one skilled in the art to produce the desired results.

[00253] Extrusion die 1800 is shown with integral precursor dispenser 1814 and graphene formation zone 1816. However, alternative embodiments of the extrusion graphene growth system can include a precursor dispenser and a graphene formation zone separate from the extrusion die. The precursor dispenser and the graphene formation zone can each be separate components or integral with each other. The placement of the individual precursor dispenser and graphene formation zone at a distance away from the extrusion die exit and in an oxygen environment can be determined by the required extrusion surface temperature and surface oxidation at time of dispensing the precursor. The surface temperature must be within the temperature range for graphene formation.

[00254] The controlled environment 1822 that includes precursor dispenser 1814 and graphene formation zone 1816 is shown as two separate areas or zones. However, alternative embodiments of the present invention may only be one zone where the precursor is dispensed into the entire zone and the graphene is grown within the same zone.

[00255] While this document describes various embodiments, the described embodiments should not be construed as limitations on the scope of any invention or of what may be claimed, but rather as descriptions of features that may be specific to particular embodiments of particular inventions. For example, any of the elements of the embodiments described herein may be combined with any of the other embodiments. Certain features that are described in this patent document in the context of separate embodiments can also be implemented in combination in a single embodiment. Conversely, various features that are described in the context of a single embodiment can also be implemented in multiple embodiments separately or in any suitable sub-combination. Moreover, although features may be described above as acting in certain combinations and even initially claimed as such, one or more features from a claimed combination can in some cases be excised from the combination, and the claimed combination may be directed to a sub-combination or variation of a subcombination.

[00256] Similarly, while operations are depicted in the drawings in a particular order, this should not be understood as requiring that such operations be performed in the particular order shown or in sequential order, or that all illustrated operations be performed, to achieve desirable results. Moreover, the separation of various system components in the embodiments described in this document should not be understood as requiring such separation in all embodiments.

[00257] Only a few implementations and examples are described and other implementations, enhancements and variations can be made based on what is described and illustrated in this document.

[00258] While the disclosure has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope of the claims. Thus, it is intended that the present disclosure cover the modifications and variations of this disclosure and their equivalents.

Claims

1. A method for fabricating graphene materials, comprising coating a semi-solid hydrocarbon precursor onto a metal substrate: heating the semi-solid hydrocarbon precursor and the coated metal substrate to a first temperature; maintaining the first temperature to dissociate the semi-solid hydrocarbon precursor into carbon on the metal substrate; and cooling to a second temperature that is lower than the first temperature to allow the dissociated hydrocarbon to arrange itself into graphene on the metal substrate.

2. The method of Claim 1 , wherein at least a portion of the semi-solid hydrocarbon precursor is petrolatum.

3. The method of Claim 1 , wherein at least a portion of the semi-solid hydrocarbon is paraffin melt.

4. The method of Claim 1 , wherein the metal substrate includes at least one of nickel, copper, or a stainless steel.

5. The method of Claim 1 , wherein the metal substrate includes one or more of a foil, a foam, a sheet, and a deposited layer.

6. The method of Claim 1 , wherein the metal substrate is substantially tubular.

7. The method of Claim 1 , further comprising pre-annealing the metal substrate before coating the semi-solid hydrocarbon precursor onto the metal substrate.

8. The method of Claim 1 , wherein heating the coated metal substrate includes heating the coated metal substrate within a chamber.

9. The method of Claim 1 , wherein at least a portion of the semi-solid hydrocarbon is petroleum jelly.

10. The method of Claim 1 , wherein the semi-solid hydrocarbon precursor includes a nitrogenous compound.

1 1. The method of Claim 10, wherein the nitrogenous compound includes one or more of pyridine, phthalocyanine, and pyrazole.

12. The method of Claim 1 , wherein the semi-solid hydrocarbon precursor includes nanoparticles of at least one of selected from the group consisting of a metal, a metalloid, and a semiconductor.

13. The method of Claim 12, wherein the metal nanoparticles include at least one of selected from the group consisting of nickel, copper, iron, gold, silver, platinum, palladium, cobalt, iridium, rhodium, osmium, and ruthenium.

14. A method for producing porous graphene comprising: coating a semi-solid hydrocarbon-nanoparticle mixture onto a surface of a metal substrate, the hydrocarbon-nanoparticle mixture including a saturated hydrocarbon and nanoparticles; heating the semi-soiid hydrocarbon-nanoparticle mixture coated metal substrate to a temperature substantially at least 450°C; maintaining the temperature of the heated semi-solid hydrocarbon-nanoparticle mixture coated metal substrate to dissociate the semi-solid hydrocarbon- nanoparticle mixture on the surface of the metal substrate into carbon and the nanoparticles; and cooling the heated semi-solid hydrocarbon-nanoparticle mixture coated metal substrate by substantially at least 20°C per minute to reach 200°C or less, wherein the cooling allows the carbon to precipitate out at the surface of the heated semi-solid hydrocarbon-nanoparticle mixture coated metal substrate and to arrange itself into graphene together with the nanoparticles; coating a polymer on the graphene and the nanoparticles; and dispersing the cooled metal substrate and the nanoparticles.

15. The method of Claim 14, wherein the polymer includes at least one of poly(methyl methacrylate) (PMMA) and poly (dimethylsiloxane) (PDMS).

16. The method of Claim 14, wherein the metal substrate is substantially tubular.

17. The method of Claim 16, wherein dispersing the cooled metal substrate and the nanoparticles includes immersing the polymer coated graphene and nanoparticles in a chemical solution.

18. The method of Claim 17, wherein the chemical solution is strongly basic or strongly acidic.

19. The method of Claim 18, wherein the strongly basic solution is potassium hydroxide (KOH) and the strongly acidic solution is hydrogen chloride (HCI) alone or in combination with ferric chloride (FeCb).

20 The method of Claim 14, wherein the nanoparticles include at least one of selected from the group consisting of copper, nickel, activated carbon, silicon, zinc oxide, tin oxide, and manganese oxide.

21. A method for incorporating metal, or semiconducting, or insulating nanoparticles during the formation a sheet of Graphene, the methods comprising the steps of: combining metal, or semiconducting, or insulating nanoparticles with a saturated hydrocarbon to form a combination; heating the combination to a predetermined temperature to obtain a melt; stirring the melt to form a substantially homogeneous mixture, transferring the substantially homogeneous mixture to a substrate; cooling the substantially homogeneous mixture to form a coated substrate; and subjecting the coated substrate to chemical vapor deposition (CVD) in an inert atmosphere to form the sheet of graphene with the metal, or semiconducting, or insulating nanoparticles incorporated therein.

22. The method according to Claim 21 , wherein the CVD includes at least one of selected from the group consisting of Thermal CVD, Hot Filament Chemical Vapor Deposition (HFCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), and Micro Wave Plasma Enhanced Chemical Vapor Deposition (MWPECVD).

23. The method according to Claim 21 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a temperature in the range of 450-1000°C.

24. The method according to Claim 21 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a pressure from 1 mT to atmospheric pressure.

25. The method according to Claim 21 , wherein the substrate includes at least one of selected from the group consisting of nickel, copper, and stainless steel.

26. The method according to Claim 21 , wherein the saturated hydrocarbon is petroleum jelly.

27. The method according to Claim 21 , wherein the saturated hydrocarbon is petrolatum.

28. The method according to Claim 21 , wherein the metal, or semiconducting, or insulating nanoparticles include at least one of selected from the group consisting of nickel, copper, iron, gold, silver, platinum, palladium, cobalt, iridium, rhodium, osmium, and ruthenium.

29. The method according to Claim 21 , wherein the metal, or semiconducting, or insulating nanoparticles include at least two of selected from the group consisting of nickel, copper, iron, gold, silver, platinum, palladium, cobalt, iridium, rhodium, osmium, and ruthenium.

30. The method according to Claim 21 , wherein the saturated hydrocarbon is soft paraffin/paraffin wax.

31. A method for incorporating dopants during the formation a sheet of graphene, the methods comprising the steps of: combining dopants with a saturated hydrocarbon to form a combination; heating the combination to a predetermined temperature to obtain a melt; stirring the melt to form a substantially homogeneous mixture, transferring the substantially homogeneous mixture to a substrate; cooling the substantially homogeneous mixture to form a coated substrate; and subjecting the coated substrate to chemical vapor deposition (CVD) in an inert atmosphere to form the sheet of graphene with the dopants incorporated therein.

32. The method according to Claim 31 , wherein the CVD includes at least one of selected from the group consisting of Thermal CVD, Hot Filament Chemical Vapor Deposition (HFCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), and Micro Wave Plasma Enhanced Chemical Vapor Deposition (MWPECVD).

33. The method according to Claim 31 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a temperature in the range of 450-1000°C.

34. The method according to Claim 31 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a pressure from 1 mT to atmospheric pressure.

35. The method according to Claim 31 , wherein the substrate includes at least one of selected from the group consisting of nickel, copper, and stainless steel.

36. The method according to Claim 31 , wherein the saturated hydrocarbon is petroleum jelly.

37. The method according to Claim 31 , wherein the saturated hydrocarbon is petrolatum.

38. The method according to Claim 31 , wherein the dopants include at least one of selected from the group consisting of lithium, beryllium, boron, nitrogen and their compounds.

39. The method according to Claim 31 , wherein the dopants include at least two of selected from the group consisting of lithium, beryllium, boron, nitrogen and their compounds.

40. The method according to Claim 31 , wherein the saturated hydrocarbon is soft paraffin/paraffin wax.

41. A method for incorporating nanostructures during the formation a sheet of graphene, the methods comprising the steps of: combining nanostructures with a saturated hydrocarbon to form a combination; heating the combination to a predetermined temperature to obtain a melt; stirring the melt to form a substantially homogeneous mixture, transferring the substantially homogeneous mixture to a substrate; cooling the substantially homogeneous mixture to form a coated substrate; and subjecting the coated substrate to chemical vapor deposition (CVD) in an inert atmosphere to form the sheet of graphene with the nanostructures incorporated therein.

42. The method according to Claim 41 , wherein the CVD includes at least one of selected from the group consisting of Thermal CVD, Hot Filament Chemical Vapor Deposition (HFCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), and Micro Wave Plasma Enhanced Chemical Vapor Deposition (MWPECVD).

43. The method according to Claim 41 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a temperature in the range of 450-1000°C.

44. The method according to Claim 41 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a pressure from 1 mT to atmospheric pressure.

The method according to Claim 41 , wherein the substrate includes at least one of selected from the group consisting of nickel, copper, and stainless steel.

46. The method according to Claim 41 , wherein the saturated hydrocarbon is petroleum jelly.

47. The method according to Claim 41 , wherein the saturated hydrocarbon is petrolatum.

48. The method according to Claim 41 , wherein the nanostructures include at least one of selected from the group consisting of nanotubes, carbon nanotubes, nano rods, nanowires, quantum dots, nano crystalline diamond (NCD), ultra nanocrystalline diamond (UNCD), and nano flakes.

49. The method according to Claim 41 , wherein the nanostructures include at least two of selected from the group consisting of nanotubes, carbon nanotubes, nano rods, nanowires, quantum dots, nano crystalline diamond (NCD), ultra nanocrystalline diamond (UNCD), and nano flakes.

50. The method according to Claim 41 , wherein the saturated hydrocarbon is soft paraffin/paraffin wax.

51. A method for incorporating additives during the formation a sheet of graphene, the methods comprising the steps of: a. providing a saturated hydrocarbon, one or more additives, and a substrate, b. applying one or more layers of the saturated hydrocarbon to the substrate, c. applying one or more layers of the one or more additives to a top surface of the one or more layers of the saturated hydrocarbon; and d. subjecting the one or more layers of the one or more additives, the one or more layers of the saturated hydrocarbon, and the substrate to chemical vapor deposition (CVD) in an inert atmosphere to form the sheet of graphene with the one or more layers of the one or more additives incorporated therein.

52. The method according to Claim 51 , wherein the CVD includes at least one of selected from the group consisting of Thermal CVD, Hot Filament Chemical Vapor Deposition (HFCVD), Plasma Enhanced Chemical Vapor Deposition (PECVD), and Micro Wave Plasma Enhanced Chemical Vapor Deposition (MWPECVD).

53. The method according to Claim 51 , wherein the step of subjecting the one or more layers of the one or more additives, the one or more layers of the saturated hydrocarbon, and the substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a temperature in the range of 450-1000°C.

54. The method according to Claim 51 , wherein the step of subjecting the one or more layers of the one or more additives, the one or more layers of the saturated hydrocarbon, and the substrate to CVD in an inert atmosphere further comprises subjecting the coated substrate to a pressure from 1 mT to atmospheric pressure.

55. The method according to Claim 51 , wherein the substrate includes at least one of selected from the group consisting of nickel, copper, and stainless steel.

56. The method according to Claim 51 , wherein the saturated hydrocarbon is petroleum jelly.

57. The method according to Claim 51 , wherein the saturated hydrocarbon is petrolatum.

58. The method according to Claim 51 , wherein the saturated hydrocarbon is soft paraffin/paraffin wax.

59. The method according to Claim 51 , wherein the one or more additives is selected from the group comprising of metal/metalloid nanoparticles, nanostructures, and dopants.

60. The method according to Claim 59, wherein the metal or semiconducting or insulating nanoparticles include at least one of selected from the group consisting of nickel, copper, iron, gold, silver, platinum, palladium, cobalt, iridium, rhodium, osmium, and ruthenium.

61. The method according to Claim 59, wherein the metal, or semiconducting, or insulating nanoparticles include at least two of selected from the group consisting of nickel, copper, iron, gold, silver, platinum, palladium, cobalt, iridium, rhodium, osmium, and ruthenium.

62. The method according to Claim 59, wherein the nanostructures include at least one of selected from the group consisting of nanotubes, carbon nanotubes, nano rods, nanowires, quantum dots, nano crystalline diamond (NCD), ultra nanocrystalline diamond (UNCD), and nano flakes.

63. The method according to Claim 59, wherein the nanostructures include at least two of selected from the group consisting of nanotubes, carbon nanotubes, nano rods, nanowires, quantum dots, nano crystalline diamond (NCD), ultra nanocrystalline diamond (UNCD), and nano flakes.

64. The method according to Claim 59, wherein the dopants include at least one of selected from the group consisting of lithium, beryllium, boron, nitrogen and their compounds.

65. The method according to Claim 59, wherein the dopants include at least two of selected from the group consisting of lithium, beryllium, boron, nitrogen and their compounds.

66. The method according to Claim 51 further comprising the steps of: e. applying additional one or more layers of the saturated hydrocarbon to a top surface of the one or more layers of the additives, and f. applying additional one or more layers of the one or more additives to a top surface of the additional one or more layers of the saturated hydrocarbon, wherein steps e and f are performed after step c and before step d.

67. The method according to Claim 66 further comprising the step of repeating steps e and f.

68. The method according to Claim 51 , wherein the step of subjecting the one or more layers of the one or more additives, the one or more layers of the saturated hydrocarbon, and the substrate to CVD in an inert atmosphere further comprises the steps: subjecting the coated substrate to a temperature in the range of 450-1000°C for a predetermined time ranging from 10 seconds to 45 minute to form a graphene sheet, and allowing nanostructure forming precursor gasses to flow for 1 to 30 minutes to form 3D nanostructures on the graphene sheet.

69. The method according to 68, wherein the nanostructure forming precursor gasses comprise hydrocarbon gasses.

70. The method according to 68, wherein the nanostructure forming precursor gasses comprise silane.

71 . The method according to Claim 21 , wherein the step of subjecting the coated substrate to CVD in an inert atmosphere further comprises the steps: subjecting the coated substrate to a temperature in the range of 450-1000°C for a predetermined time ranging from 10 seconds to 45 minutes to form a graphene sheet, and allowing gasses to flow for a predetermine time ranging from 1 to 30 minutes to form 3D nanostructures on the graphene sheet.

72. The method according to 71 , wherein the nanostructure forming precursor gasses comprise hydrocarbon gasses.

73. The method according to 71 , wherein the nanostructure forming precursor gasses comprise silane.

74. A method of fabricating graphene, the method comprising the steps of: providing a substrate transportation system, a substrate, a precursor dispenser containing one or more precursors, an energy device, and a cooling device; advancing the substrate transportation system to convey the substrate through the precursor dispenser; dispensing one or more precursors from the precursor dispenser onto the substrate; advancing the substrate transportation system to convey the substrate with the one or more precursors through the energy device; triggering the energy device to achieve one or more predetermined heating temperatures for one or more predetermined time intervals to activate the one or more precursors on the substrate: advancing the substrate transportation system to convey the substrate with the activated one or more precursors through the cooling device; triggering the cooling device to one or more predetermined cooling temperatures for one or more predetermined time intervals to form one or more graphene patterns from the activated one or more precursors on the substrate; and advancing the substrate transportation system to convey the substrate with the one or more graphene patterns for separation of the one or more graphene patterns from the substrate.

75. The method according to Claim 74, wherein the substrate transportation system and the substrate are combined as a continuous substrate connected to an unwind roll and a wind roll.

76. The method according to Claim 74, wherein the substrate transportation system and the substrate are combined as a continuous conveyor belt.

77. The method according to Claim 74, wherein the substrate transportation system comprises a conveyor belt.

78. The method according to Claim 74, wherein the step of the substrate transportation system to convey the substrate through the precursor dispenser further comprises the step of advancing the substrate transportation system at a constant rate to convey the substrate through the precursor dispenser.

79. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate through the precursor dispenser further comprises the step of advancing the substrate transportation system at an incremental rate to convey the substrate through the precursor dispenser.

80. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate through the energy device further comprises the step of advancing the substrate transportation system at a constant rate to convey the substrate through the energy device.

81. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate through the energy device further comprises the step of advancing the substrate transportation system at an incremental rate to convey the substrate through the energy device.

82. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate to the cooling device further comprises the step of advancing the substrate transportation system at a constant rate to convey the substrate through the cooling device.

83. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate to the cooling device further comprises the step of advancing the substrate transportation system at an incremental rate to convey the substrate through the cooling device.

84. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate with the one or more graphene patterns for separation of the one or more graphene patterns from the substrate further comprises the steps of: adhering a transfer strip to the one or more graphene patterns on the substrate; compressing the transfer strip and the substrate to increase adhesion between the transfer strip and the one or more graphene patterns, wherein the adhesion between the transfer strip and the one or more graphene patterns is greater than adhesion between the substrate and the one or more graphene patterns; and drawing the transfer strip in a direction away from the substrate, whereby the one or more graphene patterns are transferred to the transfer strip and separated from the substrate.

85. The method according to Claim 77, further comprising the step of pre-treating or cleaning the conveyor belt prior to the step of advancing the substrate transportation system to convey the substrate through the precursor dispenser.

86. A method of fabricating of multiple graphene patterns, the method comprising the steps of: a. providing a substrate transportation system, a substrate, two or more precursor dispensers, two or more energy devices, and two or more cooling devices, wherein each precursor dispenser of the two or more precursor dispensers contains a precursor; b. advancing the substrate transportation system to convey the substrate through a first precursor dispenser of the two or more precursor dispensers; c. dispensing a first precursor in a predetermined pattern from the first precursor dispenser of the two or more precursor dispensers on to the substrate, d. advancing the substrate transportation system to convey the substrate with the first patterned precursor through a first energy device of the two or more energy devices; e. triggering the first energy device of the two or more energy devices to a first predetermined heating temperature for a first predetermined heating time interval to activate the first patterned precursor on the substrate; f. advancing the substrate transportation system to convey the substrate with the first activated precursor through a first cooling device of the two or more cooling devices; g. triggering the first cooling device of the two or more cooling devices to a first cooling temperature for a first predetermined cooling time interval to form a first graphene pattern from the first activated precursor on the substrate; and h. advancing the substrate transportation system to convey the substrate with the first graphene pattern through one or more subsequent precursor dispensers of the two or more precursor dispensers, one or more subsequent energy devices of the two or more energy devices, and one or more subsequent cooling devices of the two or more cooling devices wherein each subsequent precursor dispenser of the one or more subsequent dispensers contains a subsequent precursor, and repeating steps c - h to form two or more graphene patterns in proximity of the first graphene pattern.

87. The method according to Claim 86, wherein the substrate transportation system and the substrate are combined as a continuous substrate connected to an unwind roll and a wind roll.

88. The method according to Claim 86, wherein the substrate transportation system and the substrate are combined as a conveyor belt.

89. The method according to Claim 86, wherein the substrate transportation system comprises a conveyor belt.

90. The method according to Claim 86, wherein a precursor of the subsequent precursor is different than the first precursor.

91. The method according to Claim 86, wherein a precursor of the subsequent precursor is the same as the first precursor.

92. The method according to Claim 86, wherein a subsequent predetermined heating temperature to activate a subsequent precursor on the substrate is different than the first predetermined heating temperature.

93. The method according to Claim 86, wherein a subsequent predetermined heating temperature to activate a subsequent precursor on the substrate is the same as the first predetermined heating temperature.

94. The method according to Claim 86, wherein a subsequent predetermined heating time interval to activate a subsequent precursor on the substrate is different than the first predetermined heating time interval.

95. The method according to Claim 86, wherein a subsequent predetermined heating time interval to activate a subsequent precursor on the substrate is the same as the first predetermined heating time interval.

96. The method according to Claim 86, wherein a subsequent predetermined cooling temperature to form a subsequent graphene pattern is different than the first predetermined cooling temperature.

97. The method according to Claim 86, wherein a subsequent predetermined cooling temperature to form a subsequent graphene pattern is the same as the first predetermined cooling temperature.

98. The method according to Claim 86, wherein a subsequent predetermined cooling time interval to form a subsequent graphene pattern is different than the first predetermined cooling time interval.

99. The method according to Claim 86, wherein a subsequent predetermined cooling time interval to form a subsequent graphene pattern is the same as the first predetermined cooling time interval.

100. The method according to Claim 74, wherein at least one precursor of the one or more precursors includes one or more dopants or nanoparticles.

101. The method according to Claim 74, wherein the step of dispensing one or more precursors from the precursor dispenser on to the substrate further comprises the step of dispensing one or more precursors from the precursor dispenser on to the substrate, wherein the one or more precursors are selected from the group consisting of at least one precursor with one or more dopants or nanoparticles and at least one precursor without one or more dopants or nanoparticles.

102. The method according to Claim 74, further comprising a dopant or nanoparticle dispenser containing one or more dopants or nanoparticles.

103. The method according to Claim 102, further comprises the step of dispensing one or more dopants or nanoparticles from the dopant or nanoparticular dispenser on to the one or more precursors after the step of dispensing one or more precursors from the precursor dispenser on to the substrate.

104. The method according to Claim 86, wherein at least one precursor dispenser of the two or more precursor dispensers includes a combination of the precursor and one or more dopants or nanoparticles.

105. The method according to Claim 86, wherein at least one subsequent precursor dispenser of the one or more subsequent precursor dispensers includes a combination of the precursor and one or more dopants or nanoparticles.

106. The method according to Claim 86, further comprising one or more dopant or nanoparticle dispenser containing one or more dopants or nanoparticles.

107. The method according to Claim 106, further comprises the step of dispensing the one or more dopants or nanoparticles from the one or more dopant or nanoparticle dispenser on to the first precursor after dispensing the first precursor in the predetermined pattern from the first precursor dispenser of the two or more precursor dispensers on to the substrate.

108. The method according to Claim 106, further comprises the step of dispensing one or more dopants or nanoparticles from the one or more dopant or nanoparticle dispenser on to a subsequent precursor after dispensing the subsequent precursor in a predetermined pattern on to the substrate from a subsequent precursor dispenser of the one or more subsequent precursor dispensers.

109. The method according to Claim 74, wherein the substrate is a catalyst substrate.

110. The method according to Claim 74, wherein the substrate is a non-catalyst substrate having a catalyst applied to the non-catalyst.

11 1. The method according to Claim 86, wherein the substrate is a catalyst substrate.

112. The method according to Claim 86, wherein the substrate is a non-catalyst substrate having a catalyst applied to the non-catalyst.

113. The method according to Claim 84, further comprises the step of supplying energy to or in proximity of at least one of the transfer strip, the substrate, or the one or more graphene patterns to at least weaken the adhesion between the substrate and the one or more graphene patterns prior to the step of drawing the transfer strip in a direction away from the substrate.

114. The method according to Claim 74, the step of advancing the substrate transportation system to convey the substrate with the one or more graphene patterns for separation of the one or more graphene patterns from the substrate further comprises the steps of: drawing the substrate in a direction away from the one or more graphene patterns, whereby the one or more graphene patterns are separated from the substrate.

115. The method according to Claim 114, further comprises the step of supplying energy to or in proximity of at least one of the transfer strip, the substrate, or the one or more graphene patterns to at least weaken the bond between the substrate and the one or more graphene patterns prior to the step of drawing the substrate in a direction away from the one or more graphene patterns.

116. A method of fabricating of graphene on an extruded part, the method comprising the steps of: a. providing an extrusion die, a precursor dispenser, and a graphene growth zone; b. supplying a non-reactant cover gas to purge reactant levels of oxygen from the precursor dispenser; c. drawing an extruded part from the extrusion die; d. advancing the extruded part through the precursor dispenser; e. dispensing at least one precursor from the precursor dispenser onto the extruded part; f. supplying a non-reactant cover gas to purge reactant levels of oxygen from the graphene growth zone; g. advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time for graphene growth on the extruded part; and h. advancing the extruded part with graphene from graphene growth zone for further processing.

1 17. The method according to Claim 1 16, wherein the precursor dispenser is integral with the extrusion die.

1 18. The method according to Claim 1 16, wherein the precursor dispenser and the graphene growth zone are integral with the extrusion die.

1 19. The method according to Claim 16, wherein the precursor dispenser and the graphene growth zone are separate components.

120. The method according to Claim 1 16, wherein the step of advancing the extruded part through the precursor dispenser further comprises the step of continuously advancing the extruded part through the precursor dispenser without stopping.

121. The method according to Claim 1 16, wherein the step of advancing the extruded part through the precursor dispenser further comprises the step of advancing the extruded part through the precursor dispenser by incremental stopping.

122. The method according to Claim 1 16, wherein the step of advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time for graphene growth on the extruded part further comprises the step of continuously advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time for graphene growth on the extruded part without stopping.

123. The method according to Claim 1 6, wherein the step of advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time for graphene growth on the extruded part further comprises the step of continuously advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time for graphene growth on the extruded part by incremental stopping.

124. The method according to Claim 1 18, wherein the integral components form a controlled environment having a sealed exit sized to receive the extruded part with graphene without allowing external gas penetration into the controlled environment during the steps of dispensing at least one precursor from the precursor dispenser onto the extruded part and advancing an extruded part with the at least one precursor through the graphene growth zone for a predetermined time period for graphene growth on the extruded part.

125. The method according to Claim 1 16, wherein the precursor dispenser and the graphene growth zone are contained within one zone.

126. The method according to Claim 74, wherein the step of advancing the substrate transportation system to convey the substrate with the one or more graphene patterns for separation of the one or more graphene patterns from the substrate further comprises the step of supplying energy to or in proximity of the substrate and the one or more graphene patterns to induce separation between the substrate and the one or more graphene patterns.

127. The method according to Claim 126, wherein the step of supplying energy to or in proximity of the substrate and the one or more graphene patterns to induce separation between the substrate and the one or more graphene patterns further comprises heating either the substrate or the one or more graphene patterns using a laser frequency depending on which material more readily absorbs the laser frequency.