Patent Grant
9776875
This is a National Phase application claiming priority to PCT/KR2012/008532 filed Oct. 18, 2012 which claims priority to Korean Application 10-2012-0039935 filed Apr. 17, 2012, Korean Application 10-2011-0128549 filed Dec. 2, 2011, and Korean Application 10-2011-0108462 filed Oct. 24, 2011, all of which are herein incorporated by reference in their entireties.
The present invention relates to a method of producing graphene using a metal catalyst.
Graphene is attracting a great deal of attention because of its excellent properties. With respect to graphene, professors Geim and Novoselov at the University of Manchester first succeeded in separating atomic layers from graphite using scotch tape in the year 2004 and were awarded the Nobel Prize for their discovery of graphene in the year 2010. In the year 2010, a roll-to-roll transfer technique of manufacturing large-area graphene having an area of 30 inches was reported, and technologies enabling graphene to be industrially applied have been continuously developed. For industrial application, graphene is required to be formed uniformly as a single layer. In the prior art, the use of general copper foils suffers from a problem in that multilayer graphene is present as islands or an epitaxial graphene layer or epitaxial graphene layers do not easily grow.
In the manufacturing of graphene electrodes, the surface energy state of a metal catalyst is important for the epitaxial growth of monolayer graphene. This is because the atomic packing density of a metal varies depending on the orientation of the metal and because factors, including dislocation density, stacking fault energy, twins and impurities, which influence the surface energy of the catalyst, influence the reaction with the gaseous molecules or atoms to be adsorbed. Particularly, when a metal has low solubility or low reactivity with the element to be adsorbed, it barely acts as a catalyst. For example, copper is frequently used for the formation of graphene thin films and has a face-centered cubic (FCC) structure. However, the solid solubility of carbon which is adsorbed onto the surface of the catalyst copper in CVD processes at 1000° C. is 0.028 at % or less. Due to this low reactivity, it is very difficult to control the adsorption of carbon atoms during the CVD processes. If structures having different orientations are present together, the energy state will become non-uniform, and thus the adsorption rate of carbon will differ between areas. This problem results in the growth of multilayer graphene in some areas to form graphite. Thus, to uniformly grow carbon on copper to form graphene thin films, it is effective to use as a catalyst a substrate which has a uniform energy state and at the same time, has formed thereon nucleation sites on which graphene nets are to be formed. Materials capable of satisfying a uniform energy state include single crystalline materials. Many studies thereon have been conducted, and particularly, studies on the use of single crystalline hexagonal FCC metals oriented in the (111) or (100) direction (for example, the study of Hori) or on single crystalline HCP metals having a (0001) plane have been conducted (J. Phys. Chem. B., Vol. 106, No. 1 15-17, 2002, Y. Hori et al.).
However, the results of the studies did not lead to industrialization, because only single crystalline metals having a size of several tens of nm can be prepared and it is impossible to obtain large areas which are industrially applicable. In addition, for industrial application, graphene is required to be formed uniformly as single layers, but the use of general copper foils in the prior art suffers from a problem in that multilayer graphene is present as islands, because the epitaxial growth rate of graphene is low.
The present inventors have developed a method for preparing a unidirectionally oriented metal catalyst for uniformly and epitaxially growing graphene and have found that the orientation and surface energy state of a catalyst substrate, particularly step structures, have a great influence on the adsorption of carbon atoms and the growth of graphene, thereby completing the present invention.
It is an object of the present invention to make the energy of a metal catalyst substrate uniform and make the surface of the catalyst substrate having unidirectionally oriented structures in order to uniformly and epitaxially grow graphene. Another object of the present invention is to provide a method for producing graphene, comprising the steps of: alloying a metal catalyst substrate to form fine step structures on the surface of the catalyst; forming step structures on the alloyed metal catalyst substrate in the atmosphere of hydrogen gas and a gas having a molecular weight higher than the atomic weight of carbon; and supplying hydrocarbon and hydrogen gases to the metal catalyst substrate.
To achieve the above objects, one embodiment of the present invention provides a method of producing graphene by forming step structures on the surface of a face-centered cubic metal catalyst substrate having the (100) or (111) orientation and supplying hydrocarbon to the substrate.
In the present invention, the metal catalyst may be a face-centered cubic metal catalyst having a cold rolling reduction ratio of 85% or higher and the (100) or (111) orientation. The metal catalyst may have a thickness of 50 μm or less. The metal catalyst may be recrystallization-annealed in a hydrogen or reducing atmosphere, cooled and then heated in an atmosphere of methane and hydrogen to grow graphene thereon. The metal catalyst may be any one selected from the group consisting of copper, silver and gold. 95% or more of the graphene is a monolayer graphene thin film. The metal catalyst may be electroplated by a pulse wave current, and the step structure may be formed by annealing at a temperature of 600° C. to 1070° C. The pulse wave current may be applied at a ratio of current supply time: rest time of 15:85 to 85:15. The pulse wave current may have a current density of 1-10 A/dm2, and the metal catalyst may be a face-centered cubic metal foil obtained by plating a metal on a cathode rotating drum. The cathode rotating drum may be polished to a roughness (Ra) of Ra 0.35 μm or less.
In addition, the metal catalyst may be alloyed with an alloying element, and the alloying element may be any one or more selected from among period 2 to period 6 elements among group 3 to group 12 transition metal elements and group 13 to 15 elements. The step structures on the metal catalyst may be formed in the atmosphere of a gas having a molecular weight higher than the atomic weight of carbon, and the metal catalyst may be aluminum, nickel, austenitic stainless steel, silver, gold or copper. The alloying element may be any one or more transition elements which have solid solubility for hydrogen or form carbides at a temperature ranging from 600 to 1060° C., and the alloying element may be any one or more selected from among aluminum, indium, silicon, silicon, germanium, tin, antimony and bismuth. The gas having a molecular weight higher than the atomic weight of carbon may be any one or more selected from among neon, argon, krypton, nitrogen, hydrocarbon, carbon dioxide, carbon monoxide and steam (H2O).
In the present invention, when viewing the surface energy of copper according to the crystalline structure, the (111) plane has the highest packing density and stable energy level among three simple planes, and the (100) plane is the next stable plane. In addition, in an actual measurement process, the (100) plane is also expressed as (200) and (001) depending on the measurement direction and position, but these can all be regarded as the same orientation.
In the present invention, the (110) plane has an open structure between two parallel arrangements of atoms, and thus is unstable compared to the (111) or (100) plane and has a structure on which a graphene net is difficult to form. For this reason, it is not suitable to use the (110) plane as a catalyst for forming a graphene mono layer.
As used herein the term “electrodeposited copper foil” refers to a copper thin film made by an electroplating process, but is limited thereto. In the present invention, the electrodeposited copper foil is prepared by carrying out electrolysis in electrolyte solution bath and electrodepositing and/or electroplating the copper ion of the plating solution onto the drum surface. Examples of the electrodeposited copper foil include a general electrodeposited copper foil having a shiny side, which is smoothly deposited on the drum surface, and a matte side opposite thereto, and a plated copper foil obtained by depositing a copper thin film on a copper foil by the electroplating process.
One embodiment of the present invention is directed to a method of making a copper foil. This method is carried out using a foil making system comprising: a container to which electrolyte solution containing copper ions is continuously supplied; a drum, a part of which is dipped and rotated in the electrolyte solution and to which a negative terminal is connected; and an anode spaced apart from the dipped part of the drum and also placed in the electrolyte solution. In this copper foil making system, an electric current is applied between the cathode rotating drum and the anode to continuously electrodeposit copper ions on the drum surface.
In one embodiment of the present invention, if the roughness (Ra) of the drum surface is more than 0.35 μm, it will be transferred to the electrodeposited copper foil so that graphene will be non-uniformly and excessively produced as multilayered area in a CVD process.
In one embodiment of the present invention, if the thickness of an oxide layer on the drum surface is less than 1 nm, the separating force of an electrodeposited copper will increase provably to damage the copper foil, and if the thickness of the oxide layer is more than 20 nm, electrolysis current density will be excessively required, resulting in decreased productivity.
In one embodiment of the present invention, the drum is made of titanium or stainless steel, which is generally used for the fabrication of electrodeposited copper foils. In addition, it may be made of carbon steel, alloy steel, non-ferrous metals, ceramic materials or composite materials. In addition, any material may be used for the drum, as long as it can coat cubic structure metal by means such as deposition, plating or spraying.
In another embodiment of the present invention, a plated copper foil is provided by pulse-current plating copper and controlling the foil to a single orientation by annealing. Also, a rolled copper foil is provided by cold-rolling a copper foil at a reduction ratio of 85% or more and controlling the foil to a single orientation by annealing. On these copper foils, graphene is easily grown.
In one embodiment of the present invention, there is provided graphene fabricated by the above method.
In the present invention, the catalyst substrate preferably has a hexagonal lattice structure having a single orientation so that uniform and epitaxial graphene is grown thereon. Importantly, the surface of the catalyst substrate is smooth when viewed macroscopically and has a step structure when viewed microscopically. The catalyst substrate preferably has the (111) and/or (100) orientation. As shown in
In one embodiment of the present invention, if the stacking fault energy of the catalyst substrate is reduced or lattice distortion increases by alloy element addition, dislocations or twins are likely to occur in the material to increase the internal energy. Thus, alloying is carried out such that step structures are easily formed during annealing. Unlike this, in metals having high stacking fault energy, dislocations attract each other and cross-slip easily occurs so as to reduce the dislocation density and thus reduce the internal energy of the material. Thus, in the present invention, when an alloying element is added to reduce the stacking fault energy, twins are likely to occur during annealing at high temperature. The twin sites have higher surface energy so that graphene growth becomes easy, and thus larger graphene crystals can be obtained. The alloying element is an element which has hydrogen solid solubility or forms carbides at a temperature of 600˜1060° C. at which graphene can be synthesized. Specifically, it is selected from among period 2 to period 6 elements among group 3 to 12 transition elements and group 13, 14 and 15 elements. The hydrogen solid solubility of elements at 1000° C. is 70.5 ppm for copper, 4.5 ppm for gold, 22.4 ppm for silver, 2.6 ppm for chromium, 1.2 ppm for molybdenum, 32.8 ppm for manganese, 186.2 ppm for cobalt, 251 ppm for iron, 562.3 ppm for nickel, 7079 ppm for rhodium, 4.7 ppm for platinum, 11879 ppm for titanium, and 85.1 ppm for aluminum. This suggests that transition metals have solid solubility for hydrogen In the case of elements other than transition metals, aluminum of group 13 has high solid solubility, and indium binds with hydrogen at high temperature to form a compound. Among group 14 and 15 elements, silicon makes carbides, and germanium, tin, antimony and bismuth form hydrogen compounds, like indium. Thus, the alloying elements described in the present invention may mostly be added.
In one embodiment of the present invention, as the reduction ratio of a copper foil increases and the thickness of a copper foil decreases, dislocations increase, and the rotation of recrystallized grains in an annealing process can be facilitated. It was found that 95% or more of the area of a copper foil which was cold-rolled at a reduction ratio of 85% or more had the (100) orientation after annealing. Thus, in order to obtain a structure having a single orientation, a copper foil can be rolled at a reduction ratio of 85% or higher to a thickness of 50 μm or less.
Copper has low stacking fault energy, and thus when it is cold-rolled, the dislocation density thereof is increased to cause atomic migration and diffusion during annealing. Herein, the atoms migrate by an image force acting between dislocations during heating at high temperature and finally disappear while leaving step structures corresponding to Burgers vectors on the surface. As the stacking fault energy and flow stress of the catalyst copper alloy decrease and the cold reduction ratio thereof increases, dislocation movement in the material becomes more active to facilitate the formation of step structures. The step structures which are formed in atomic layer units in the Burgers vector size by this dislocation movement are formed so small even at a high temperature of 1000° C. such that they so weakly adsorb gas molecules. For this reason, in the present invention, a gas, such as argon or nitrogen, which has a molecular weight higher than the atomic weight of carbon while having low chemical reactivity with a copper foil, is supplied together with small amount of hydrogen during an annealing process, so that the gas molecules collide with the copper surface by the Brown motion even at a temperature of about 600° C. to assist in the migration of copper atoms, thereby facilitating the formation of step structures. Unlike areas in which impurity elements or alloying elements exist as compounds, step structures are distributed uniformly throughout the catalyst surface, and thus form an environment in which graphene grows epitaxially.
In one embodiment of the present invention, hydrogen serves to maintain the reducing atmosphere, and thus it is added in an amount corresponding to less than 40% of the flow rate of the gas after draw-air out for an annealing chamber. In the graphene synthesis process following the annealing process, hydrogen also serves to control the growth rate of graphene, because the decomposition rate of hydrocarbon decreases as the ratio of hydrogen increases. The flow rate of the gas is in the range of 0.1-10 sccm/μm, and it can be increased as the thickness of a copper foil increases, and it is decreased with increases in temperature and the molecular weight of the gas.
The step structures act as nucleation sites, and thus adsorb hydrocarbons to produce carbon radicals serving as graphene nuclei. Once graphene nuclei are produced, carbon radicals around the nuclei bind to the surrounding carbon radicals or directly adsorb hydrocarbon to form carbon-carbon bonds, thereby growing graphene.
On a unidirectionally oriented metal catalyst prepared according to the present invention, graphene can be grown uniformly and epitaxially.
Moreover, a method for producing graphene according to the present invention can form monolayer graphene by epitaxially growing graphene while increasing the growth rate of graphene.
Hereinafter, the present invention will be described in detail with reference to examples and test examples. It is to be understood, however, that these examples are for illustrative purposes and are not intended to limit the scope of the present invention.
Tough pitch copper foils (a purity of 99.9% or more, an oxygen content of 0.05% or less) having thicknesses of 0.5 mm and 0.2 mm were annealed, and then cold-rolled to thicknesses of 12 μm, 25 μm, 40 μm, 50 μm and 100 μm. The cold-rolled foils were heated at various annealing temperatures so that 95% or more thereof was oriented in the (100) direction. It was confirmed that a graphene thin film was evenly formed on the annealed foils (see
As can be seen in Table 1 above, when the foils were cold-rolled at a reduction ratio of 85% or more, 95% or more the area thereof was oriented in the (100) direction, and when the foils were recrystallization-annealed, graphene layer could be formed on the copper foils. Also, it can be seen that, when the reduction ratio is high and the thickness of the copper foil is small, the (100) orientation is easily formed. Thus, the rolled copper foil provided according to the present invention has a critical significance when it has a reduction ratio of 85% or more or a thickness of 50 μm or less.
The foils were recrystallization-annealed at various temperatures in an atmosphere of hydrogen having a flow rate of 10 sccm, followed by cooling, and the orientation thereof was measured. Then, the foils were heated to 1000° C. and maintained in an atmosphere of 15 sccm methane and 10 sccm hydrogen for 30 minutes while graphene was grown thereon by CVD.
2-1: Fabrication of Electrodeposited Copper Foil by Pulse-Current Plating and Graphene Layer
Plain tough pitch copper foils were air-stirred in a solution composed of 180-330 g/L of copper sulfate pentahydride (CuSO4.5H2O), 40-120 g/L of sulfuric acid and 40-120 ppm of hydrochloric acid at a temperature of 30˜55° C. and a current density of 1-10 A/dm2, thereby pulse current plating the foils. The results are shown in
As can be seen therein, in the plated state, the (200) single orientation or a mixed orientation of (111) (200) (220) orientations can appear depending on the plating conditions, but after the growth of graphene at 1000° C., only the (200) orientation appears. Also, when the pulse current plated specimens were annealed, the mixed orientation was arranged to the (200) orientation at 600° C. or higher regardless of the plating conditions. However, even at the above current density range, the mixed orientation appeared even after annealing, when plating was carried out by a PR (pulse-reverse) method or direct current plating.
It appears that the reason why the single orientation is determined depending on the waveform of current even at the same current density is that the pulse wave shows a high atomic packing density compared to other current waves while providing epitaxial electrodeposition, and thus the mixed orientation is arranged to a single orientation by subsequent heating. With respect to another reason, in the manufacturing of general electrodeposited copper foils, plating is carried out at high current density and a high rate of about of 1 m/min, and thus the degree of disorder of deposited copper atoms is high such that the orientation thereof is difficult to rearrange to a single orientation by the introduction of heat energy during annealing.
Thus, the scope of the present invention includes pulse-plating a copper foil by stirring in a solution composed of 180-330 g/L of copper sulfate pentahydride (CuSO4.5H2O), 40-120 g/L of sulfuric acid and 40-120 ppm of hydrochloric acid at a temperature of 30˜55° C. and a current density of 1-10 A/dm2, and annealing the pulse-current plated copper foil at a temperature of 600° C. or higher, and also growing graphene on the plated copper foil.
2-2: Fabrication of Electrodeposited Copper Foil and Graphene Layer
Copper scrap was dissolved in acid solution, and the solution was supplied into an opening below an anode placed in an electrolysis bath containing 250 g/l of copper sulfate (CuSO4.H2O) and 80 g/l of sulfuric acid at 30° C., while an electrolysis reaction (cathode electrode current density: 8 A/dm2) was induced so that a thin copper foil having a (111) orientation was electrodeposited on a titanium (Ti) rotating drum having a connector to cathode. Herein, the foil side facing the drum side was shiny, and the opposite side was matte. The drum surface was polished to a roughness (Ra) of 0-0.35 μm and anodized to form an oxide layer of 1-20 nm in order to facilitate the separation of an electrodeposited copper foil from the polished drum surface.
Copper was pulse-current plated on the electrodeposited copper foil according to the method of Example 2-1, and graphene was deposited and grown thereon by CVD. The resulting structure was observed with an optical microscope and the orientation thereof was measured by XRD (see
A copper alloy foil containing 140 ppm of silver (see
It can be seen that, when graphene was formed on copper, graphene islands and carbides were formed, but on the silver-containing copper alloy, graphene was epitaxially formed. However, when copper was previously annealed at 800° C. to form steps, graphene was epitaxially formed thereon.
The above copper alloy and copper had a hexagonal lattice structures having the (111) or (100) orientation after annealing, and these catalyst substrates also had the same orientation in the following examples.
Thus, it could be seen that the addition of a substitutional alloy to copper provides graphene nucleation sites and promotes the development of a step structure to suppress carbide formation and also enables the epitaxial growth of graphene.
A 18 μm thick copper alloy foil containing 3.2% nickel, 1.5% silicon and 0.4% magnesium was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen to form steps structure, and graphene was synthesized thereon by CVD at 800° C. for 30 minutes in an atmosphere of a mixed gas of 70 sccm methane and 10 sccm hydrogen (see
As a control, a 25-μm thick copper foil containing no alloy element was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen to form a step structure, and graphene was synthesized thereon by CVD at 800° C. for 30 minutes in an atmosphere of a mixed gas of 70 sccm methane and 10 sccm hydrogen (see
As can be seen in
Thus, when a step structure is sufficiently developed, graphene can be synthesized by reducing the concentration of hydrogen gas or shortening the synthesis time.
As can be seen in
As a control for the graphene prepared in Example 4, copper foil was annealed at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 50 sccm argon and 10 sccm hydrogen, and graphene was synthesized thereon by CVD at 1000° C. for 30 minutes in an atmosphere of a mixed gas of 15 sccm methane and 10 sccm hydrogen. The results are shown in
Meanwhile,
In addition, it was found that, even when CVD synthesis was carried out at 1000° C. for 1 second in an atmosphere of a mixed gas of 30 sccm methane and 10 sccm hydrogen, well developed step structures and formed graphene nuclei (see
While the invention has been described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiments disclosed for carrying out this invention, but that the invention will include all embodiments falling within the scope of the present application.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2011-0108462 | Oct 2011 | KR | national |
| 10-2011-0128549 | Dec 2011 | KR | national |
| 10-2012-0039935 | Apr 2012 | KR | national |
| Filing Document | Filing Date | Country | Kind |
|---|---|---|---|
| PCT/KR2012/008532 | 10/18/2012 | WO | 00 |
| Publishing Document | Publishing Date | Country | Kind |
|---|---|---|---|
| WO2013/062264 | 5/2/2013 | WO | A |
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|---|---|---|---|
| 7479590 | Kuczynski | Jan 2009 | B1 |
| 20030019755 | Hey | Jan 2003 | A1 |
| 20110195207 | Hong | Aug 2011 | A1 |
| 20110290380 | Okayama | Dec 2011 | A1 |
| Number | Date | Country |
|---|---|---|
| 100116253 | Mar 1997 | KR |
| 1020090103985 | Oct 2009 | KR |
| 1020110006644 | Jan 2011 | KR |
| 1020110051584 | May 2011 | KR |
| 2010055612 | May 2010 | WO |
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| Fan, Lili, et al., “Step driven competitive epitaxial and self-limited growth of graphene on copper surface”, AIP Advances 1, (2011), 032145-1 to 032145-9. Dec. 31, 2011. |
| Gao, Li, et al., “Epitaxial Graphene on Cu(111)”, Nano Lett., 10, 3512-3216. Aug. 2, 2010. |
| Number | Date | Country | |
|---|---|---|---|
| 20140290565 A1 | Oct 2014 | US |
