WO2013191347A1 - Device for continuously producing graphene - Google Patents

Abstract

Disclosed is a device for continuously producing graphene. The device for continuously producing graphene, according to the present invention, continuously synthesizes the graphene in a deposition chamber which supplies a carbon precursor to a catalyst substrate, and comprises: an uncoiler for continuously supplying the catalyst substrate; a coiler for continuously receiving the catalyst substrate that is supplied from the deposition chamber; and a low shell for accommodating the deposition chamber, the uncoiler, and the coiler. According to the present invention, the graphene is uniformly synthesized on the catalyst substrate inside the deposition chamber, design for vacuum and exhaust is rendered easy, and heat efficiency can be increased.

Description

Continuous Graphene Manufacturing Equipment

The present invention relates to a graphene manufacturing apparatus, and more particularly, to a graphene manufacturing apparatus capable of continuously producing a large amount of graphene by a roll-to-roll method.

Graphene was already predicted by Hanns-Peter Boehm in 1962, but it wasn't until 2004 that the team of Geim and Novoselov at the University of Manchester used scotch tape to remove layers of atomic units from graphite. I succeeded in separating. Later, in 2005, the results of his experiments with graphene's team on Fermi Dirac's statistics on particles that followed Fermi Dirac's statistics were solved. Previously, the monoatomic graphene was expected to have low melting point due to its inability to maintain its shape in nature and to be thermodynamically unstable, but in reality it showed very stable and excellent crystallinity.

Graphene consists of two triangular sublattices, each of which has different electrical properties, forming a hexagonal grating lattice. More Looking at yes Three of the four outermost electrons out of carbon constituting the pin is sp ² hybrid orbital (sp ² hybrid orbitals) the formed forms a strong covalent bond of sigma (σ) bond the remaining one electron is near It forms a graphene net by forming a pi (π) bond with another carbon. At this time, the electrons between the carbon atoms jump and move through atoms of the same property, and the moving speed is 20,000-50,000 cm 2 / Vs, which is 100 times faster than Si semiconductor, and has a low electric resistance, resulting in low heat generation. In addition, when manufacturing on a ribbon, it is possible to manufacture functional graphene having semiconductor characteristics through edge control effects or through nanopatterning and doping. Its mechanical properties are excellent, and its breaking strength is 125GPa, which is 100 times that of steel and twice that of diamond. In addition, the 10cm size graphene film is stretched enough to not lose its electrical properties even when it is pulled 10%, so it is not easily broken. have. In 2010, technologies that can be utilized in the industry are continuously being developed, such as the roll-to-roll method, which manufactures the world's largest 30-inch large-area graphene.

It is important to uniformly implement the graphene thin film in a single layer in order to use industrially, but the prior arts have a problem that it is not suitable to mass-produce large-area products by providing a roll-to-roll continuous synthesis method using quartz tubes.

And Korean Patent Laid-Open No. 10-2012-0001591 discloses "graphene manufacturing apparatus and manufacturing method", specifically, a gas supply unit for supplying a gas containing carbon, and a gas for heating the gas supplied from the gas supply unit And a deposition chamber in which a heating unit, a substrate having a catalyst layer is disposed, and an introduction tube for introducing a gas of the gas heating unit into the deposition chamber, whereby the temperature of the deposition chamber is lower than the temperature of the gas heating unit. Since it can be set, the selection range of the catalyst metal which can be used for a catalyst layer becomes wider, and the damage of a board | substrate by high temperature heat can be minimized.

However, the graphene manufacturing apparatus according to Korean Patent Laid-Open No. 10-2012-0001591 merely provides an idea of passing the metal foil through roll-to-roll, and thus does not provide a concept or method of a specific apparatus necessary for industrialization. There is. For example, due to the catalyst foil passing through the deposition chamber, there is no choice but to provide openings on both sides. However, the present invention does not provide a specific airtight method of blocking the external atmosphere and maintaining vacuum or pressure.

Sony Material Research Institute announced the roll-to-roll CVD synthesis technology using Joule's heat at the 73rd academic lecture of the Japan Society for Applied Physics (JSAP) held at Ehime University on September 11-14. This method has the advantage that the catalyst copper foil is directly heated by electrical resistance in only a few seconds and the heat transfer is low elsewhere in the apparatus. However, it is difficult to increase the gap between heating rolls due to the characteristics of the Joule heat heating method. For this reason, it is difficult to improve the temperature variation for each site and the nonuniformity of the synthesis conditions due to the short heating time. Therefore, the inventors have improved the electrical conductivity by doping the gold chloride to graphene to overcome this. However, metal doping improves conductivity but acts as an impurity, and thus has a disadvantage of acting as a cause of oxidation or poor aging over time.

Prior to this invention, the inventors of the present invention have found that the orientation and surface energy state of the catalyst substrate, in particular the step structure, have a great influence on the adsorption of carbon atoms and graphene growth. Step structures have already been observed by graphene researchers, but their production mechanisms and processes are not yet known. The inventors have determined that these step structures are determined by a number of factors, including stacking fault energy, annealing temperature, atomic filling rate depending on orientation, dislocation density and twin depending on processing conditions. It was confirmed that the present invention was a continuous synthesis apparatus capable of uniform graphene synthesis using step formation.

An object of the present invention is to provide a graphene manufacturing apparatus to reduce the exhaust capacity burden and improve the thermal efficiency, as well as to promote the catalytic action in the deposition chamber and to achieve uniform nucleation and shortening of the deposition time.

The above object is, in the graphene manufacturing apparatus for synthesizing the graphene continuously in the deposition chamber for supplying the carbon precursor to the catalyst substrate, an uncoiler for continuously supplying the catalyst substrate; A coiler that receives the catalyst substrate continuously from the deposition chamber; And a shell containing the deposition chamber, the uncoiler and the coiler.

Accordingly, the catalyst substrate is subjected to a graphene deposition process in the order of the uncoiler, the deposition chamber, and the coiler, and the uncoiler, the deposition chamber, and the coiler are arranged clockwise or counterclockwise.

The carbon precursors are decomposed to provide carbon radicals, such as carbon monoxide, methane, ethane, ethylene, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, nucleic acid, cyclohexane, ethane hole, methane hole, It provides a gaseous state any one selected from the group consisting of benzene, toluene, camphor, coal dry gas, shale gas, and combinations thereof.

The continuous graphene manufacturing apparatus according to the present invention includes a first heating line for maintaining annealing temperature above the recrystallization temperature of the catalyst substrate and a first gas supply line for forming a gas atmosphere having a molecular weight of at least carbon atoms. It may further comprise a step forming chamber to form a step structure on the surface of the catalyst substrate.

In the deposition chamber, a second heating wire for maintaining a temperature of 600 ~ 1100 ℃, a second shielding material to surround the heat or magnetic field of the second heating wire and a second gas supply line for supplying a carbon precursor to the catalyst substrate Is provided.

The first heating wire and the second heating wire are installed parallel to the moving direction of the catalyst substrate, and induction heating coils, metal filaments, radiant tubes, joule heating elements such as graphite heating elements, and infrared rays Both lamps can be used.

Inside the step forming chamber and the deposition chamber, a shielding material may be formed to reflect the heat or to block the magnetic field of the induction heating coil that is formed for insulation or the outside. At this time, the shielding material for blocking the magnetic field of the induction heating coil uses a silicon steel sheet, an amorphous film laminate or a soft magnetic powder sintered material such as Ferrotron, Fluxtrol or SMC, and is installed in the opposite direction of the desired magnetic field.

The second heating wire is an induction heating coil, the second shielding material may be made of any one or more of silicon steel sheet, amorphous film laminated material, iron-based soft powder powder sintered material.

The second heating wire is an electrical resistance heating wire, the second shielding material is made of any one of stainless steel sheet, titanium plate, heat-resistant tempered glass, quartz, pyrolytic boron nitride, pyrolytic graphite, gold mica, silicon carbide, alumina, magnesia, zirconia Or a mixture thereof.

The continuous graphene manufacturing apparatus according to the present invention includes an accommodating chamber accommodating the uncoiler and the coiler and formed adjacent to the deposition chamber, and the rochelle surrounds the accommodating chamber and the deposition chamber to form a closed space. The shell is formed of a double wall structure, and is filled with a vacuum or heat insulating material between the double walls.

The receiving chamber is provided with an inner wall to protect the catalyst substrate from indirect heating by a heating unit.

In the deposition chamber, a cylindrical deposition drum in which the catalyst substrate is in close contact is formed.

In the deposition chamber, a deposition roll is formed to guide the catalyst substrate to closely contact the deposition drum at a predetermined interval.

At the inlet and the outlet of the deposition chamber, a speed sensor for sensing the moving speed of the catalyst substrate is formed, and the rotation speed of the coiler and the uncoiler is controlled by the speed sensor.

Continuous graphene manufacturing apparatus according to the present invention, the restructured gas tank to store the restructured gas supplied into the deposition chamber; A carbon precursor tank in which a carbon precursor supplied into the deposition chamber is stored; And a hydrogen tank in which hydrogen supplied into the deposition chamber is stored, and the reorganization gas and hydrogen are selectively supplied.

In addition, in the continuous graphene manufacturing apparatus according to the present invention, a recovery device is formed so that the gas exhausted from the deposition chamber is recovered to the restructured gas tank, carbon precursor tank, and hydrogen tank, respectively.

A break detection sensor is formed inside the deposition chamber to detect break of the catalyst substrate.

At least one of the inlet and the outlet of the deposition chamber is provided with a buffer unit for releasing the tensile force applied to the catalyst substrate in the deposition chamber.

The catalyst substrate is one or more of the transition element or group 13-15 elements having hydrogen solubility or forming carbides in the range of 600 to 1060, or an alloy thereof, among which aluminum, nickel, iron, stainless steel, silver , Gold or copper. An alloying element is added to the catalyst substrate to lower stacking defect energy or to promote decomposition of hydrogen or carbon, and the alloying element also has a hydrogen solubility or a transition element or a group 13 to 15 element that forms carbide. It consists of one or more.

The reorganization gas is made of any one or more of nitrogen, neon, argon, krypton, xenon, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia and water vapor.

In the continuous graphene manufacturing apparatus according to the present invention, the catalyst substrate is overlapped in two layers, the gas having a molecular weight of at least the first heating wire and carbon atoms to maintain the annealing temperature or more of the recrystallization temperature of the two or more overlapped catalyst substrate A first gas supply line is provided on both sides of the catalyst substrate to form an atmosphere, and includes a step forming chamber for forming a step structure on the catalyst substrate. A second heating line for maintaining a temperature of 1100 ° C and a second gas supply line for supplying hydrocarbon gas to both sides of the catalyst substrate through the step forming chamber are provided.

The first gas supply line and the second gas supply line are disposed on both sides of the catalyst substrate overlapped in two layers.

The catalyst substrate is transferred in the longitudinal direction in the step forming chamber and the deposition chamber.

The buffer part includes a press roll formed at the outlet of the deposition chamber, and the press roll is formed to rotate at no load while pressing in order not to damage the catalyst substrate.

The buffer unit includes a press roll formed at an inlet or an outlet of the deposition chamber, and the press roll has a step formed at both ends to serve as a guide for contacting only part of both ends of the catalyst substrate or supporting only both sides.

The buffer unit includes driving rolls respectively formed at the inlet and the outlet of the deposition chamber, and the driving roll rotates while contacting the catalyst substrate and the speed is synchronized with each other. Accordingly, the tensile force applied to the catalyst substrate being heated is minimized.

When the second heating wire is an induction heating coil, a distance between the catalyst substrate and the induction heating coil is within 10 mm, more preferably 2 to 3 mm. In addition, the induction heating frequency is made of a high frequency of 10kHz or more, thereby forming a shallow magnetic field and high efficiency is advantageous for sheet heating.

The outer surface of the catalyst substrate discharged from the deposition chamber is not in contact with another object or coated with a protective film before being wound on the coiler.

The outlet of the deposition chamber is formed such that the catalyst substrate is discharged along the tangent of the deposition drum.

According to the present invention, the uncoiler, the deposition chamber, and the coilers are formed in a continuous type that interlocks with each other, thereby achieving a compact structure, easily designing for vacuum and exhaust, and increasing thermal efficiency.

In addition, by performing a step forming process prior to the deposition process, a nano unit step is formed on the entire surface of the catalyst substrate prior to the formation of graphene, thereby using a catalyst substrate that facilitates physical adsorption of precursor gas (carbon compound). As a result, catalysis can be promoted and uniform nucleation and deposition time can be shortened.

1 is a view showing a state in which a step is formed on the catalyst substrate of the metal which has been subjected to the step forming process according to the present invention;

2 is a schematic view showing an atomic arrangement of copper and a substituted element alloy state;

3 is a graph showing the results of graphene synthesis by CVD using methane as a carbon precursor for 30 minutes at 600 ℃ in a copper and copper alloy catalyst,

4 is a graph showing the results of graphene synthesis by CVD using methane as a carbon precursor at 800 ° C. for 30 minutes at a copper and copper alloy catalyst.

5 is a view showing the results of graphene growth by forming a step on the surface of the copper and copper alloy catalyst,

6 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus according to an embodiment of the present invention,

FIG. 7 is a perspective view schematically showing a catalyst substrate, a second heating wire, and a second shielding material in the continuous graphene manufacturing apparatus shown in FIG. 6;

8 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus according to another embodiment of the present invention,

9 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus according to another embodiment of the present invention,

10 is a view schematically showing some components of a continuous graphene manufacturing apparatus according to another embodiment of the present invention,

11 is a view schematically showing some components of a continuous graphene manufacturing apparatus according to another embodiment of the present invention,

12 is a view schematically showing some components of a continuous graphene manufacturing apparatus according to another embodiment of the present invention,

13 is a view schematically showing a part of the configuration of the continuous graphene manufacturing apparatus according to another embodiment of the present invention,

14 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus according to another embodiment of the present invention,

15 is a view schematically showing some components of a continuous graphene manufacturing apparatus according to another embodiment of the present invention,

16 is a view showing a process of forming graphene using a continuous graphene manufacturing apparatus according to the present invention,

17 is a view schematically showing some components of a continuous graphene manufacturing apparatus according to another embodiment of the present invention,

18 is a view schematically showing some components of a continuous graphene manufacturing apparatus according to another embodiment of the present invention.

Explanation of symbols on main parts of drawing

1: continuous graphene manufacturing apparatus 10: step forming chamber

11: first heating line 12: first gas supply line

13 step roll 14 first shielding material

15: preheating unit 16: step drum

17: exhaust port 20: deposition chamber

21: second heating wire 22: second gas supply line

23: exhaust port 24: second shielding material

25: preheating unit 26: cooling unit

27: deposition drum 28: deposition roll

30: uncoiler 40: coiler

50: Rochelle 53: exhaust pump

60: speed detection sensor

70: break detection sensor 71: light emitting unit

72: light receiver 80: step sensor

90: recovery device 100: film supply device

110: step gas tank 120: reorganized gas tank

130: carbon precursor tank 140: hydrogen tank

150: receiving chamber 151: exhaust port

160: buffer portion 161: pressure roll

162: drive roll 163: pendulum guide

164: dancer roll

200: catalyst substrate 300: transfer film

V: Valve M: Flow Meter

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, in describing the present invention, descriptions of already known functions or configurations will be omitted to clarify the gist of the present invention.

FIG. 1 is a view showing a state in which a step is formed in a catalyst substrate 200 of a metal that has passed through a step forming chamber 10 according to the present invention, and FIG. 2 schematically shows an atomic arrangement of copper and a state of a substituted element alloy. 3 is a graph showing the results of graphene synthesis by CVD using methane as a carbon precursor at 600 ° C. for 30 minutes in a copper and copper alloy catalyst, and FIG. 4 shows methane of copper and a copper alloy at 800 ° C. for 30 minutes. Is a graph showing the results of synthesizing graphene by CVD using carbon as a precursor, and FIG. 5 is a diagram showing the results of graphene growth by forming a step on the surface of copper and a copper alloy catalyst, and FIG. 6 is an embodiment of the present invention. 2 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus 1 according to the example.

In the cyclic graphene manufacturing apparatus 1 according to the present invention, before synthesizing the graphene on the catalyst substrate 200 in the deposition chamber 20, the step of the nano unit on the entire surface of the catalyst substrate 200 in the step forming process It is a main technical feature that the step is formed, and accordingly, the formation of the step and the relationship between the step and graphene in the present invention will be described first.

In the present invention, in order to obtain a uniform and epitaxial graphene in the catalyst substrate 200, it is preferable to have a single orientation of a lattice structure with high filling rate. The catalyst substrate is made of any one or more of transition elements or groups 13 to 15 elements having a hydrogen solubility or forming carbides in the range of 600 ~ 1060 ℃, especially aluminum, nickel, iron, stainless steel, silver, gold Or copper. Macroscopically, it is important to have a step structure in the microscopic surface state of nano units, and it is preferable that the surface index of the catalyst substrate 200 is a single orientation of (111) or (100). The step structure of the present invention is a stepped structure developed from the atomic unit smaller than the micron unit as shown in Figs. 3 (b) and 5. There are mainly four types of steps found by the inventors (FIG. 1). It is a multi-cube in which a stepped paddy step Paddy step and a ledge that makes a planar bend alternately on a plane, a ratchet of a serrated shape, and a cube cube are stacked. It developed when annealing the cold rolled thin plate with high rolling reduction at 600 ° C. or higher to supply a gas having a mass of carbon atom weight (12 g / mol) or more.

2 is a view simulating the state of the copper alloy to which the atomic arrangement and substituted alloy element is added when only copper is present in the present invention. (a) shows the atomic arrangement of copper, and (b) and (c) show the atomic arrangement states of the solid solution alloy to which a substituted element with a larger atomic diameter than copper is added and the solid solution alloy to which a small element is added. As shown in (b) and (c), when there is a difference in atomic radius, lattice distortion and lattice strain exist around the substituted atoms, which leads to an energy imbalance. The interatomic connection around the substitutional element is a line representing this lattice deformation state. These lattice strains in copper alloys cause dislocations and lamination defects in the course of physical external stresses such as rolling. These dislocations, stacking defects, and twins are more likely to develop into steps during the annealing process. Because the step structures act as nucleation sites, they produce carbon radicals that form graphene nuclei by adsorption and thermal decomposition of carbon precursors at high temperatures. Once the carbon radicals are produced, they bond with the surrounding carbon radicals and grow into graphene nuclei with carbon-carbon bonds.

In one embodiment of the present invention, the alloy is performed to easily form a step structure after annealing because the internal energy is high, since the dislocation defect energy of the catalyst substrate 200 is lowered or the lattice strain is increased to easily cause dislocations or twins within the material. . On the other hand, in metals with high lamination defect energy, even when cold worked, dislocations are attracted to each other and cross-slip easily occurs, resulting in lower dislocation densities, thereby lowering internal energy of the material and forming steps. When an alloying element is added to the catalyst substrate, annealing twinning is easily generated at high temperature, and the twinned portion has a high surface energy, thereby obtaining larger graphene crystals under the same conditions. Such a catalyst substrate promotes the gas phase decomposition reaction of hydrogen or carbon precursor at the front of the substrate, thereby inducing uniform nucleation. The alloying element is a transition element that has hydrogen solubility or forms a carbide in the range of 600 to 1060 ° C., which is a temperature at which graphene can be synthesized, that is, two cycles among Group 3 to Group 12 transition metals and Group 13, 14 and 15 elements. Elements belong to 6 cycles. The approximate hydrogen solubility of each element is 70.5ppm copper, 4.5ppm gold, 22.4ppm silver, chromium 2.6ppm, molybdenum 1.2ppm, manganese 32.8ppm, cobalt 186.2ppm, iron 251ppm, nickel 562.3ppm, rhodium 7079ppm, 4.7 ppm of platinum, 11879 ppm of titanium, and 85.1 ppm of aluminum. This suggests that most transition metals have high solubility in hydrogen. In addition, elements other than transition metals, that is, aluminum in Group 13, have a high hydrogen utility, and indium has a strong bonding strength to bond with hydrogen at high temperature to form a compound. Of the 14 and 15 elements, silicon makes carbides and germanium, tin, antimony and bismuth form hydrogen compounds like indium. Therefore, most of the alloying elements of the present invention can be added.

In one embodiment of the present invention, the higher the reduction ratio and the thinner the thickness of the copper foil, the more the potential increases and may facilitate the rotation of the recrystallized particles during the high temperature annealing process. After annealing in the cold rolled copper foil with a reduction ratio of 85% or more, it was confirmed that the sheet was rotated to (100) single azimuth plane. Therefore, in order to obtain a single orientation texture, it can be processed to 85% or more in reduction ratio and 50 µm or less in thickness.

Copper has low lamination defect energy and cold processing increases the internal dislocation density, which causes atomic movement and diffusion during annealing. As it is heated to a high temperature, it moves to an image force acting between dislocations, and finally disappears, leaving a stepped structure as a Burgers vector on the surface. The lower the stacking defect energy, the flow stress, and the lower the cold reduction rate of the catalytic copper alloy, the more active the dislocation movement in the material, thereby easily forming a step structure. However, the step structure of the atomic layer unit formed to the size of Burgers vector by the dislocation transfer is too small and formed smoothly even at a high temperature of 1000 ° C, which is insufficient to adsorb and decompose gas molecules. Therefore, in the present invention, when the step gas having a molecular weight of more than carbon atoms, such as argon or nitrogen, and having a low chemical reactivity with copper is supplied with hydrogen in the atmosphere during annealing, the gas molecules are brown at high temperature even at a temperature of about 600 ° C. This impinges on the surface of copper and facilitates atomic movement, facilitating the formation of step structures. Unlike the parts where impurity elements or alloying elements exist as compounds, the steps are uniformly distributed throughout the catalyst surface, thus creating an environment in which graphene is epitaxially grown.

In one embodiment, the amount of hydrogen is sufficient to maintain a reducing atmosphere, so that after the vacuum is maintained, it is added at about 10-40% of the gas flow rate. In the graphene synthesis process after annealing, the higher the proportion of hydrogen, the slower the decomposition rate of the carbon precursors, thereby controlling the graphene growth rate. The gas flow rate may be increased as the thickness of the copper foil increases in the range of 0.1 to 10 sccm / µm, and is decreased as the temperature is high or the atomic weight is large.

Because these step structures act as nucleation sites, they adsorb carbon precursors to produce carbon radicals that become graphene nuclei. Once the graphene nucleus is formed, the carbon radicals in the nucleus bind to the surrounding carbon radicals or directly act as a catalyst for adsorbing and decomposing carbon precursors, thereby rapidly growing graphene with carbon-carbon bonds.

Example 1 Formation of Graphene on a Copper Alloy Catalyst Substrate

Graphene was formed by heating 140 ppm of silver-added copper alloy (see (b) of FIG. 3) at 600 ° C. and methane 70 sccm and hydrogen 10 sccm for 30 minutes, and as a control, copper (FIG. ) Was confirmed whether or not graphene is formed under the same conditions (see FIG. 3).

Graphene islands and carbides are formed when graphene is grown on copper, but graphene is epitaxially grown on copper alloys containing silver. However, graphene was epitaxially grown when copper formed a step structure while annealing at 800 ° C. in advance.

The copper alloy and copper have a single orientation of hexagonal lattice structure (111) or (100) after annealing, and the catalyst substrate 200 has the same orientation in the following embodiments.

Therefore, it can be seen that addition of a substitutional alloy to copper promotes the development of the step structure at the same time as the graphene nucleation site, thereby inhibiting carbide formation and enabling epitaxial graphene growth.

Example 2 Checking the Effect of Step Structure Formation

An 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 argon 50sccm and hydrogen 10sccm in a mixed gas atmosphere to form a sufficient step structure, and methane 70sccm at 800 ° C for 30 minutes. Graphene was synthesized by CVD in a 10 sccm mixed hydrogen atmosphere (see FIG. 4 (a)).

As a control, 25 µm thick copper without an alloying element was annealed at 1000 ° C. for 30 minutes in an atmosphere of 50 sccm of argon and 10 sccm of hydrogen mixed gas to form a step structure. Graphene was synthesized (see FIG. 4 (b)).

FIG. 4 (a) shows the diamond particles covered with the multi-layered graphene on the copper alloy, and FIG. It can be seen that carbon radicals are rapidly produced from copper alloy foil, although 800 ℃ is lower than the conventional CVD graphene synthesis temperature of 1000 ~ 1060 ℃. If step structure is formed on copper foil, graphene grows even at low temperature. It was.

Therefore, when the step structure is sufficiently developed, graphene may be synthesized by reducing the concentration of the carbon precursor gas or shortening the time. In addition, in the case of excessive generation of carbon radicals as shown in FIG. 4 (a), the amount of alloys can be reduced to 1 atomic% or less, or the carbon precursor gas concentration and synthesis time can be reduced to obtain single-layer graphene, as shown in FIG. 4 (b). When the concentration of the gas is too high, the production of carbon radicals is faster than graphene growth, so it can be seen that in addition to graphene growth at the nucleation sites, triangular, square plate-shaped diamonds, rod-shaped, and granular diamonds grow. Even in this case, the graphene was synthesized by lowering the concentration of carbon precursors or increasing the concentration of hydrogen gas to obtain single layer graphene. Through this study, the present inventors found that step structure formation greatly contributes to the formation of monolayer graphene by promoting graphene growth rate as well as carbon radical production.

Example 3 Graphene Growth Confirmation on Catalyst Substrates with Various Alloying Elements

As a control, in FIG. 5 (a), copper was annealed at 1000 ° C. for 30 minutes in argon 50sccm and hydrogen 10sccm mixed gas atmosphere, and graphene was synthesized by CVD while supplying 15sccm in methane and 10sccm in hydrogen at 1000 ° C. for 30 minutes.

On the other hand, in Figure 5 (b) the silver alloy of 80ppm alloy copper alloy annealed in an atmosphere of argon 20sccm, hydrogen 10sccm mixed gas at 800 ℃ for 30 minutes, graphene by CVD while supplying 20sccm, hydrogen 10sccm for 5 minutes at 1000 ℃ 5 (C) is 40 ppm of chromium, (d) is 200 ppm of iron, (e) is 130 ppm of cobalt, (f) is 100 ppm of nickel, and (g) of FIG. ) Is an alloy containing 140 ppm of silver and 70 ppm of silicon, annealed in a mixed gas atmosphere of argon 50 sccm and hydrogen 10 sccm at 1000 ° C. for 30 minutes at 1000 ° C., and 20 sccm of methane and 10 sccm of hydrogen at 800 ° C. for CVD. Graphene is synthesized. Both of them have well developed step structures and graphene have grown epitaxially. At this time, the graphene has a transparent characteristic because it is easy to be formed in a single layer and excellent in light transmittance. The darker shades are not attached to the catalyst and are excited, or because the step structure under the graphene changes due to grain boundaries or twins, the electrons are absorbed or diffusely reflected, making them appear blacker.

Hereinafter, a graphene manufacturing apparatus according to the present invention will be described in detail.

6 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus 1 according to an embodiment of the present invention, Figure 7 is a catalytic substrate in the continuous graphene manufacturing apparatus 1 shown in FIG. 200 is a perspective view schematically illustrating the second heating wire 21 and the second shielding material 24, and FIG. 8 schematically illustrates a configuration of the continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention. 9 is a view schematically showing the configuration of the continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention, Figure 10 is a continuous graph according to another embodiment of the present invention FIG. 11 is a view schematically showing some components of the pin manufacturing apparatus 1, and FIG. 11 is a view schematically showing some components of the continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention.

The continuous graphene manufacturing apparatus 1 according to the present invention is for mass production of graphene by a roll-to-roll method, and includes an uncoiler 30, a coiler 40, a deposition chamber 20, a rochelle 50, and the like. And a reorganization gas tank 120, a carbon precursor tank 130, and a hydrogen tank 140 to accommodate each gas used to form graphene.

In addition, in the continuous graphene manufacturing apparatus 1 according to the present invention, the catalyst substrate 200 is preheated to the preheated portion 25 and the catalyst passed through the deposition chamber 20 before flowing into the deposition chamber 20 The cooling part 26 which cools the board | substrate 200 is provided. The preheater 25 may be formed separately from the deposition chamber 20. Alternatively, the preheater 25 may be formed by dividing the deposition chamber 20 into stages.

The uncoiler 30 is a part at which manufacturing starts in the circulating graphene manufacturing apparatus 1 according to the present invention, is formed in a drum shape, and the catalyst substrate 200 is wound around the outer circumferential surface thereof. 40 is a catalyst substrate 200 on which graphene is wound.

At the edges of the uncoiler 30 and the coiler 40, a portion having an extended diameter in the form of a flange may be formed to stably support the catalyst substrate 200, and may be made of ceramic and / or metal.

In addition, the uncoiler 30 and the coiler 40 are provided with a motor (not shown) for rotation and the like for controlling the rotation speed in order to continuously supply and wind the catalyst substrate 200. A control unit (not shown) and a reduction gear (not shown) are provided.

In the continuous graphene manufacturing apparatus 1 according to the preferred embodiment of the present invention, as shown in FIG. 10, the uncoiler 30 and the coiler 40 are accommodated together in the accommodating chamber 150, thereby accommodating the chamber 150. ) And the deposition chamber 20 may be formed in a form having two compartments, the catalyst substrate 200 is formed in the form of circulating the receiving chamber 150, the deposition chamber 20 in order. That is, the catalyst substrate 200 passes through the uncoiler 30, the deposition chamber 20, and the coiler 40 in order, and the uncoiler 30, the deposition chamber 20, and the coiler 40 rotate clockwise. Or counterclockwise.

The deposition chamber 20 is adjacent to the receiving chamber 150 and shares a wall with the receiving chamber 150. A slit-shaped gap for moving the catalyst substrate 200 may be formed on a wall shared by the deposition chamber 20 and the accommodation chamber 150.

The deposition chamber 20 is to allow the deposition of carbon in the interior, the second heating wire 21 for heating to maintain a temperature of 600 ~ 1100 ℃ that the graphene can be deposited is formed therein, A second gas supply line 22 is formed through which the carbon precursor gas supplied from the carbon precursor tank 130 is injected.

The deposition chamber 20 is provided with a cylindrical deposition drum 27 in which the catalyst substrate 200 is in close contact. The catalyst substrate 200 introduced into the deposition chamber 20 is in close contact with the deposition drum 27 and passes through the deposition chamber 20 in a form of circulating the deposition drum 27. However, not only the catalyst substrate 200 rotates while the deposition drum 27 is fixed, the catalyst substrate 200 is in close contact with the outer circumferential surface of the deposition drum 27, and the catalyst substrate 200 and the deposition drum 27 are together. It is preferable to be conveyed in a rotating form.

In the deposition chamber 20, a deposition roll 28 is formed to guide the catalyst substrate 200 to closely contact the deposition drum 27 at a predetermined interval. That is, the deposition roll 28 supports the catalyst substrate 200 to rotate together with the deposition drum 27 without being spaced in close contact with the deposition drum 27.

In the present invention, by forming the rotary deposition drum 27 in the deposition chamber 20, so as to ensure sufficient time and space for the formation of graphene even in a relatively narrow space compared to the linear transfer means do.

In addition, since the deposition is performed while the catalyst substrate is brought into close contact with the outer circumferential surface of the deposition drum 27, the precursor gas (carbon compound) is introduced into the back surface of the catalyst substrate 200 (the surface in contact with the deposition drum 27). You can prevent it. In the case of controlling the gas flow as described above, a process of treating with expensive plasma etching equipment to remove the graphene grown on the rear surface of the catalyst substrate 200 can be omitted, thereby improving productivity and reducing costs.

The overall material of the deposition chamber 20 and the deposition drum 27 is heat resistant tempered glass, quartz, pyrolytic boron nitride, It may be made of inorganic materials such as pyrolytic graphite, phlogopite mica, silicon carbide (SiC), alumina, magnesia, zirconia, or metals such as stainless steel, nichrome steel, and invar.

8 is a view schematically showing some components of the vertical and double-sided continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention, Figure 9 is a continuous graph according to another embodiment of the present invention 4 is a view schematically illustrating the buffer unit 160 and the cooling unit 26, which are part of the fin manufacturing apparatus 1.

The preheating part 15 of the step forming chamber, the preheating part 25 and the cooling part 26 of the deposition chamber are in contact with the catalyst substrate 200 or transmit radiant heat to the catalyst substrate 200 or to the catalyst substrate 200. It may be made in various ways by injecting a heated or cooled fluid, it may be formed in a roll form, a box form, a slot form and the like.

For example, when formed in a roll shape, the catalyst substrate 200 is formed to pass between the rolls provided in pairs and disposed in close proximity to each other, and intervening elastic means for allowing the rolls to be elastically supported toward the catalyst substrate 200. The roll (preheater 15, etc.) can serve as a guide. The preheating unit 15 and the preheating unit 25 formed as described above may be formed separately from the step forming chamber 10 and the deposition chamber 20, or may be formed inside the step forming chamber 10 and the deposition chamber 20. It may be made in the form of forming the step roll 13 or the deposition roll 28.

In addition, the cooling unit 26 is formed to circulate the refrigerant therein so as to rapidly cool by conduction when it comes into contact with the catalyst substrate 200, or install a gas supply line for injecting cooling gas to the catalyst substrate 200. It can be formed in the form of spraying. In this case, the cooling gas may be supplied by a separate supply means, and may be supplied branched from the restructure gas tank 120 or the hydrogen tank 140. The cooling gas suppresses abnormal reaction of the formed graphene, increases the strength of the catalyst substrate 200, and allows the catalyst substrate 200 to be stably wound on the coiler 40.

12 is a view schematically showing a part of the configuration of the continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention, Figure 13 is a continuous graphene manufacturing apparatus (1) according to another embodiment of the present invention FIG. 14 is a diagram schematically illustrating some components of FIG. 14, and FIG. 14 is a diagram schematically illustrating a configuration relationship of a continuous graphene manufacturing apparatus 1 according to another exemplary embodiment of the present invention.

12, 13, and 14, when the step forming chamber 10 is included in the rochelle 50 together, the second heating line 21 is formed adjacent to the inner surface of the deposition chamber 20 and the deposition drum. (27) It may be formed in a shape surrounding the periphery. The second heating wire 21 is installed to be heated close to the catalyst substrate as shown in FIG. As shown in Figure 11 (a), the second heating wire 21 can be formed continuously, as shown in Figure 11 (b), divided into a plurality of temperature to manage the temperature for each section by section temperature It can be managed uniformly so that does not change. The second heating wire 21 is repeatedly installed along the moving direction of the catalyst substrate, and includes induction heating coils, metal filaments, radiant tubes, joule heating elements such as graphite heating elements, and infrared lamps. And the like can all be used.

A second shielding material 24 is formed on the outside of the catalyst substrate and the second heating wire 21 in contact with the outer circumferential surface of the deposition drum 27, and the heat generated by the second heating wire 21 is transferred to the deposition chamber 20. Be focused. In addition, a second heating wire 21 facing outward may be installed on the inner surface of the deposition drum. In this case, a shielding material may be installed behind the second heating wire 21 to prevent heat from being lost to the center of the drum, thereby improving efficiency. However, when the induction heating coil is heated outside the deposition drum using the induction heating coil, the induction magnetic field is directed toward the drum, so that the shielding material may be omitted from the second heating wire 21 installed outside the deposition drum 27.

The second gas supply line 22 should be such that the carbon precursor, the reorganization gas and the hydrogen gas are uniformly sprayed on the catalyst substrate 200 so as not to generate a position where carbon radicals are depleted. Accordingly, the catalyst in the deposition chamber 20 The center of the second gas supply line 22 is disposed at the center of the deposition surface of the substrate 200. In addition, the second heating line 21 and the second gas supply line 22 may be provided in plural along the moving direction (circumferential direction) of the catalyst substrate 200, and the plurality of second gas supply lines 22 By adjusting the installation position, the size of the gas flow path and the injection angle of the gas supply line, it is possible to smooth the gas flow by causing a difference in the gas supply amount and flow rate injected from each second gas supply line 22.

The reorganization gas is supplied into the deposition chamber 20 through the reorganization gas tank 120, and in the present invention, the reorganization gas includes reorganization of a defect such as an unstable five-angle, seven-angle graphene or a cavity of the catalyst substrate 200. Healing) or assists the doping gas to react well, and may be composed of argon, helium, neon, krypton, xenon, nitrogen, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia, hydrogen compounds, water vapor and the like.

Hydrogen supplied into the deposition chamber 20 through the hydrogen tank 140 controls the generation rate of carbon radicals.

In the continuous graphene manufacturing apparatus 1 according to the present invention, the shell 50 surrounds the deposition chamber 20 to form a closed space, the carbon precursor, reorganization gas, and hydrogen supplied into the deposition chamber 20. By maintaining the pressure of the deposition chamber 20 formed by partial pressure, such as higher than the pressure of the shell 50, it is possible to prevent other gas from flowing into the deposition chamber 20, so that the flow of the precursor gas (carbon compound) It is done smoothly.

In the present invention, atmospheric pressure chemical vapor deposition (AP-CVD) may be performed to maintain graphene growth by maintaining the pressure inside the deposition chamber 20 at atmospheric pressure, and further, the pressure inside the deposition chamber 20 may be reduced. Low pressure chemical vapor deposition (LP-CVD) may be performed.

In addition, an exhaust port 23 through which each gas supplied into the deposition chamber 20 is discharged is formed in the deposition chamber 20. The exhaust port 23 may be formed in the deposition chamber 20 itself, or alternatively, may be formed in the accommodation chamber 150 connected to the deposition chamber 20. In the latter case, the gas inside the deposition chamber 20 is moved to the receiving chamber 150 and then exhausted through the exhaust port 151. In the step forming chamber 10 to be described later, an exhaust port 17 through which each gas supplied into the step forming chamber 10 is discharged is formed. The exhaust port 17 may be formed in the step forming chamber 10 itself, or may be exhausted through the exhaust port 151 formed in the accommodation chamber 150.

In the present invention, the step forming chamber 10 may be installed between the uncoiler 30 and the deposition chamber 20 for growing the graphene, so that the step gas is introduced into the step forming chamber 10. By doing so serves to help the graphene is uniformly and quickly formed on the catalyst substrate 200.

12, 13, and 14, when the step forming chamber 10 is formed, the deposition chamber 20 and the accommodation chamber 150 are adjacent to each other, and the deposition chamber 20 and the accommodation chamber 150 and the wall are formed. Share. On the wall shared by the step forming chamber 10 and the receiving chamber 150, a slit-shaped gap for moving the catalyst substrate 200 may be formed. As shown in FIG. 13, the step forming chamber 10 may be formed. In the case where the catalytic substrate 200 passes directly through the deposition chamber 20, the slit-shaped gap for the movement of the catalyst substrate 200 is also formed on the wall shared by the step forming chamber 10 and the deposition chamber 20. Can be formed.

In the step forming chamber 10, a first heating line 11 is formed to be maintained at an annealing temperature of the catalyst substrate 200 or higher, and the step gas supplied from the step gas tank 110 is formed. The first gas supply line 12 injected after inflow is formed.

In addition, the step forming chamber 10 is provided with a cylindrical step drum 16 to which the catalyst substrate 200 is in close contact. The catalyst substrate 200 introduced into the step forming chamber 10 is in close contact with the step drum 16 and passes through the step forming chamber 10 in a form of circulating the step drum 16. Operation of the step drum 16 is performed in the same manner as the deposition drum 27 described above. In the step forming chamber 10, a step roll 13 is formed to guide the catalyst substrate 200 to be in close contact with the step drum 16 at a predetermined interval. That is, the step roll 13 supports the catalyst substrate 200 to rotate together with the step drum 16 without being spaced in close contact with the step drum 16. By forming the rotating step drum 16 in the step forming chamber 10, it is possible to secure sufficient time and space for step formation even though the space is relatively narrow compared with the linear transfer means.

The material of the step forming chamber 10 and the step drum 16 may be made of heat-resistant tempered glass, quartz, pyrolytic boron nitride, pyrolytic graphite, and gold, as in the deposition chamber 20 described above. It may be made of inorganic materials such as mica (Phlogopite mica), silicon carbide (SiC), alumina, magnesia, zirconia, or metals such as stainless steel, nichrome steel, and Invar.

The step forming chamber first heating line 11 has the same structure and functions the same as the deposition chamber second heating line 21. In addition, a first shielding material 14 is formed outside the step-forming first heating wire 11, that is, between the inner surface of the step-forming chamber 10 and the first heating wire 11, and the first heating wire ( Heat by 11) is concentrated in the direction of the center of the step forming chamber 10.

The first gas supply line 12 for forming a step may include a first gas supply line in the center of the outer circumferential surface of the catalyst substrate 200 in the step forming chamber 10 such that the step forming gas is uniformly injected onto the catalyst substrate 200. 12) to be centered. In addition, the first gas supply line 12 may be provided in plural along the moving direction (circumferential direction) of the catalyst substrate 200, and the installation positions of the plurality of first gas supply lines 12 and holes in the gas supply line. By adjusting the size and the injection angle, it is possible to smooth the gas flow by causing a difference in the gas supply amount and the flow rate injected from each first gas supply line 12.

In general, when observed with a high-magnification electron microscope, it can be seen that there are nano-curves (NRA = Nano Ripples Array) inside the annealing twin. The catalyst substrate 200 having a low lamination defect energy such as copper accumulates in the crystal when cold worked. The stress is relieved while forming twins in the crystal and recrystallization during annealing. However, there is not enough energy to act as a driving force of the annealing twin, so that the twin is formed only in a part of the crystal, so that the step structure as in the present invention is not formed on the entire surface of the catalyst substrate. In addition, in graphene growth using the copper catalyst substrate 200, the carbon solubility of copper is low and defects such as inclusions, grain boundaries, or scratches present on the surface of the catalyst substrate are nucleated by physical adsorption. Graphene nucleation is likely to be uneven because it acts as a site first.

In order to solve this problem, in the present invention, a step gas (for example, a catalyst substrate 200 made of copper) having a mass of about 20% or more relative to the atomic weight of the main element constituting the catalyst substrate 200 during annealing. ), A gas having a mass of carbon atom or more, and neon, nitrogen, carbon monoxide, carbon dioxide, argon, krypton, xenon, ammonia, water vapor, etc.) collides with the metal atoms of the catalyst substrate 200 in a Brownian motion to assist the movement of atoms Steps in nano units are formed on the entire surface of the substrate 200.

When the stepping process is performed on the catalyst substrate 200, the steps of tens to hundreds of nanometers are uniformly formed to act as nucleation sites, thereby facilitating physisorption of the precursor gas (carbon compound) on the catalyst surface. It promotes catalysis, and as a result, graphene uniform nucleation and precursor gas decomposition rate increase effect can be obtained.

In addition, the deposition time may be shortened due to the step formation, and the deposition temperature may be lowered. When the deposition temperature is lowered, the strength of the catalyst substrate 200 increases, thus preventing the cutting of a separate carrier film (catalyst substrate 200). And a film for supporting) is unnecessary.

The step forming chamber 10 is supplied with a gas for reducing oxide film from the hydrogen tank 140 in addition to the step gas. Oxide film reduction gas is a reducing gas having a low oxidation water, that is, gases such as hydrogen or carbon monoxide, ammonia, hydrogen sulfide, hydrogen compounds that can replace it.

In the present invention, the shell (50) is formed surrounding the uncoiler (30), the step forming chamber (10), the deposition chamber (20), and the coiler (40) to form a closed space. That is, the accommodation chamber 150, the step forming chamber 10, and the deposition chamber 20 may be formed by dividing the inside of the shell 50 into three zones. The shell 50 may be formed of a single wall structure, but the shell 50 according to a preferred embodiment of the present invention is formed of a double wall structure, and is filled with a vacuum or heat insulating material between the double walls. Alternatively, the refrigerant may be circulated between the double walls. According to the structure (double wall structure) of the rochelle 50 formed as described above, heat is prevented from being emitted to the outside of the rochelle 50, and the cooling of the catalyst substrate 200 on which graphene is synthesized is maintained by keeping the internal temperature low. You can do that.

Currently, the deposition chambers proposed for graphene production assume a quartz tube low pressure and vacuum chamber for CVD and should have a vacuum sealing accordingly, and the vacuum of the chamber is allowed while allowing the continuous supply of the catalyst substrate 200. Not only is it difficult to maintain the sealing, but even if the sealing has the problem that the structure and equipment will be complicated. In addition, in order to maintain a vacuum at the exit side of the deposition chamber, it is difficult to maintain airtightness by a roller type or any sealing means, and the graphene composite layer of the catalyst substrate 200 is damaged.

In the present invention, in order to solve this problem, since the shell 50 is formed around the uncoiler 30, the step forming chamber 10, the deposition chamber 20 and the coiler 40 to form a closed space. In order to solve the problem of sealing, low-pressure deposition can be effectively performed in the deposition chamber 20 and the vacuum substrate can be maintained in the catalyst substrate 200 to prevent the graphene composite layer from being damaged.

In addition, when the uncoiler 30, the step forming chamber 10, the deposition chamber 20, and the coiler 40 are circulated, the chambers form a compact structure in which the chambers are in close contact with each other. The maintenance can be made more easily and the waste space can be reduced, thereby reducing the amount of gas supplied and reducing the burden of exhaust.

In the deposition chamber 20, the carbon precursor tank 130, the reorganization gas tank 120, and the hydrogen tank 140 are connected through pipes (toward the second gas supply line 22). Mass flow controller (M) and valve (V) are formed.

And step gas chamber 110 and the hydrogen tank 140 is connected to the step forming chamber (10) through the pipe (connected toward the first gas supply line 12), each pipe also has a flow meter for flow control ( M) and the valve V are formed.

Outside the rochelle 50, a recovery device 90 is formed so that the gas exhausted from the rochelle 50 is recovered into the restructured gas tank 120, the carbon precursor tank 130, and the hydrogen tank 140, respectively.

The recovery device 90 may be configured in the same form as a known gas recovery device 90, and may be used to decompose and classify carbon precursors through a gas filter and a catalyst. Through the recovery device 90, the waste gas discharged through the exhaust pump 53 of the Rochelle 50 is collected, filtered, and classified, thereby classifying the gas into step gas, restructure gas, and carbon precursor according to purity and composition. It may be formed to circulate toward the tank 110, the reorganization gas tank 120 and the carbon precursor tank 130.

As described above, according to the present invention, the accommodating chamber 150, the step forming chamber 10, and the deposition chamber 20 are formed in a cyclical form in close contact with each other to achieve a compact structure and to easily design for vacuum and exhaust. It is possible to increase the thermal efficiency.

At the outlet of the step forming chamber 10, a step sensor 80 is formed on the catalyst substrate 200 to detect whether a step is formed. The step sensor 80 measures the pulse wave generated due to lattice relaxation while the step is formed on the catalyst substrate 200 or the phase transformation due to the difference in the electromagnetic resistance at both sides of the entrance and exit of the step forming chamber 10. It can be made by measuring the optical difference (for example, reflectance) according to the electromagnetic or step formation to detect the.

The inlet and outlet of the deposition chamber 20 is formed with a speed sensor 60 for detecting the moving speed of the catalyst substrate 200. The speed sensor 60 is connected to a control unit for controlling the rotation of the coiler 40, so that the rotational speed of the coiler 40 is controlled. While the graphene is manufactured, the catalyst substrate 200 passes through the first preheating unit 15, the step forming chamber 10, the second preheating unit 25, the deposition chamber 20, and the cooling unit 26. Since thermal expansion and contraction are caused, and the diameter (diameter in the wound state) of the catalyst substrate 200 wound around the coiler 40 increases, when the coiler 40 rotates at a constant speed, the deposition chamber ( The moving speed of the catalyst substrate 200 passing through 20 is changed or gradually increased. In view of this point, in the present invention, the speed sensor 60 is installed to detect the moving speed of the catalyst substrate 200 at the inlet and the outlet of the deposition chamber 20 and thereby the rotational speed of the coiler 40. By controlling, the moving speed of the catalyst substrate 200 can be synchronized.

The speed sensor 60 is made of a non-contact sensor using an electric or magnetic such as a tachometer, a Hall Effect sensor, an Eddy current sensor, or an RF speed sensor. Can be.

In the circulating graphene manufacturing apparatus 1 according to the present invention, a film supply for allowing the transfer film 300 to be applied after the catalyst substrate 200 having passed through the deposition chamber 20 is cooled through the cooling unit 26. Device 100 may be formed. The film supply device 100 is provided with the uncoiler 30 and the coiler 40 in the receiving chamber 150, installed in parallel with the coiler 40, and coated with the transfer film 300. The substrate 200 is wound around the coiler 40. Transfer film 300 may be made of PMMA, PET, PVDF, PEN, MS, PS, PC, COP, PES, PI, FRP, and the like, the graphene deposited catalyst substrate 200 is deposited chamber 20 It is applied in the process of winding through the cooling unit 26 while leaving the transfer film 300 is bonded. The first dummy part of the substrate wound on the coiler 40 is applied without the graphene being deposited, but the graphene is coated with the part that comes out while the deposition process is performed. Where the film and the substrate are combined, as shown in FIGS. 13 and 14, a pressure roll is installed to bring the transfer film 300 into close contact with the catalyst substrate 200.

In the step forming chamber 10 and / or the deposition chamber 20, a break detection sensor 70 for detecting break of the catalyst substrate 200 is formed.

As illustrated in FIG. 9, the break detection sensor 70 may be formed in the form of a laser sensor or an infrared sensor in the step forming chamber 10 and the deposition chamber 20, and the light emitting unit 71 and the light receiving unit 72. ) Can be separated. The light emitting unit 71 is positioned on one side of the catalyst substrate 200, the light receiving unit 72 is positioned on the other side, and when the breakage of the catalyst substrate 200 occurs, the light emitted by the light emitting unit 71 receives the light receiving unit ( In 72) it can be made in the form of detecting the break.

In addition, the break detection sensor 70 may be formed in the form of the above-described speed sensor 60, not in the form of the optical sensor described above. As mentioned above, at the inlet and the outlet of the deposition chamber 20, a speed sensor 60 for detecting the moving speed of the catalyst substrate 200 is formed, the inside of the deposition chamber 20 of the catalyst substrate 200 When the break is made, the speed is reduced or the speed becomes '0' at the inlet side as compared with the outlet side of the deposition chamber 20, through which the breakage of the catalyst substrate 200 can be detected.

In addition, the break detection may be made in the form of detecting the load applied to the coiler 40. When the breakage of the catalyst substrate 200 occurs, the load on the coiler 40 is drastically reduced, and the breakage detection may be performed by detecting this.

15 (a) and 15 (b) are diagrams schematically showing some components of the continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention.

In the present invention, the buffer unit 160 is formed at the inlet and / or outlet of the deposition chamber 20 to form a pair of the pressure roll 161 and the driving roll 162 to control the transfer speed of the catalyst substrate 200. . At this time, the pressing roll 161 in contact with the graphene forming surface of the catalyst substrate 200 has a structure synchronized with the driving roll 162 to rotate without load while lightly pressing the catalyst substrate 200, or both ends of the pressing roll 161 By giving a step to the middle can be formed to serve as a guide for supporting only a portion of both ends or only both sides without contacting the graphene composite layer. The driving roll 162 generates friction and transfers the frictional force while contacting the lower surface of the catalyst substrate 200 so that the pressure roll 161 does not apply sliding stress or excessive tensile force to the graphene layer, thereby causing breakage of the catalyst substrate or damage to the graphene layer. Can be prevented.

In addition, as shown in (b) of FIG. 15 (b), pressure rollers 161 and driving rolls 162 which rotate while contacting the catalytic substrate 200 are respectively installed at the inlet and the outlet of the deposition chamber 20 to increase the speed of these rolls. When synchronized, the catalytic substrate 200 in the chamber can minimize the tension between these drive rolls 162 by thermal expansion, and the other drive rolls 162 or guide rods that rotate in series with the drive rolls 162. It is possible to minimize the tension applied to the catalyst substrate 200 by forming a buffer portion between the rolls.

In the present invention, by installing a buffer section according to the buffer unit 160 at the inlet and / or outlet of each heating line (11, 21) by not interlocking with the drive roll 162 of the next step in the heating line (11, 21) Only a minimum tension may be applied to the catalytic substrate 200. In this case, excessive local tension that can occur when interlocking with the next step without a buffer section can be prevented.

If there is no buffer unit 160, when the catalyst substrate 200 is pulled out by the driving force from the outlet of the step forming chamber 10, the tension acts to the uncoiler 30 through the inlet of the step forming chamber 10, thereby stepping. Tension may be applied to the catalyst substrate 200 heated in the forming chamber 10 to cause a cutting accident.

At this time, as in the present invention, the catalyst substrate 200 is provided between the step forming chamber 10 inlet and the uncoiler 30 by installing the buffer unit 160 combined with the pressure roll 161 and the driving roll 162. When a buffer section that can be stacked is formed, tension is applied to the catalyst substrate 200 in the first heating line 11 to a minimum.

The same effect can be obtained by providing a buffer section between the step forming chamber 10 and the deposition chamber 20 and between the deposition chamber 20 and the coiler 40. In addition, by inserting a light weight dancer roll 164, the substrate flows smoothly in the buffer section, and a moderate tension is applied to the substrate, thereby maintaining the flatness of the substrate in the chamber. In particular, when a device such as a pendulum guide (163, pendulum guide) is additionally installed in the buffer section between the deposition chamber 20 and the coiler 40, the catalyst section 200 is stacked, and thus the buffer section can serve as a cooling unit. After the strength of the catalyst substrate 200 is sufficiently restored, there is an advantage that can be wound around the coiler 40.

FIG. 16 is a view illustrating a process of forming graphene using the continuous graphene manufacturing apparatus 1 according to the present invention, and FIG. 17 is a continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention. Figure is a schematic diagram showing a part of the configuration.

The double-sided graphene manufacturing method according to the present invention, as shown in Figure 16, 17 comprises a bonding step (S10), forming step (S20), cooling step (S30) and separation step (S40).

The coupling step (S10) is to overlap the two catalyst substrates 200 so that both ends are coupled, and to prevent the carbon precursor gas from penetrating into the catalyst substrate 200 to be coupled. However, since the two overlapped catalyst substrates 200 are to be separated after graphene is formed, the inner surfaces of the overlapped catalyst substrates 200 do not need to be bonded or bonded to each other.

Forming step (S20) is a process for forming graphene, graphene is formed by supplying carbon precursor gas to both sides (outer side) of the catalyst substrate 200 in an atmosphere of 600 ~ 1100 ℃ temperature is maintained Be sure to After the graphene is formed, a cooling step S30 is performed to cool the catalyst substrate 200.

After cooling the catalyst substrate 200 on which graphene is formed, a catalyst substrate in which both surfaces are coated with the film 300 is obtained. After the separation of the two catalyst substrates 200 coupled to both ends through slitting (not shown), etc., it is possible to simultaneously obtain two catalyst substrates 200 having graphene formed on one surface thereof. Separation of the two catalyst substrates 200 may also be achieved by removing only the portion (edge portion) joined by a conventional cutter. As described above, according to the present invention, it is possible to form two sheets (graphed or continuous) of the catalyst substrate 200 on which graphene is formed in one process.

In addition, when graphene is generally formed on a catalyst layer composed of a single layer, the graphene must be treated with an expensive plasma etching equipment to remove graphene grown on the rear surface of the catalyst substrate (opposite to the graphene formation surface). In the present invention, since such a step can be omitted, productivity and cost reduction effects can be obtained.

The graphene manufacturing apparatus 1 according to the present invention is such that the graphene is formed on the outer surface of the two-layered catalyst substrate 200 while the two-layered catalyst substrate 200 is introduced into the apparatus. Except as specifically limited in the present invention, the term "catalyst substrate" refers to a catalyst substrate stacked in two layers.

The deposition chamber 20 illustrated in FIGS. 6, 14, and 15 is formed long in the horizontal direction (moving direction of the catalyst substrate 200 in the horizontal direction), but is not limited thereto. As shown in FIG. 17, it may be formed in a longitudinal direction or an inclined direction. In particular, when the deposition chamber 20 is formed in the longitudinal direction, even if the length of the catalyst substrate 200 is increased by thermal expansion inside the deposition chamber 20, the movement path may be kept constant. (In the horizontal direction, when the catalyst substrate 200 is increased by thermal expansion, there is a problem that it is difficult to maintain the horizontal.)

In addition, when the second gas supply line 22 is formed on both sides of the overlapped catalyst substrate 200, when the deposition chamber 20 is placed in the horizontal direction, the catalyst substrate 200 is struck by gravity in a heated state and is lowered. Since the graphene forming surface may be damaged while the second gas supply line 22 and the catalyst substrate 200 are in contact with each other, the deposition chamber 20 may be placed in a longitudinal direction, preferably in a longitudinal direction or an inclined direction. In this case, such damage can be prevented.

18 is a view schematically showing some components of the continuous graphene manufacturing apparatus 1 according to another embodiment of the present invention.

The outer surface (the outer surface on which graphene is formed) of the catalyst substrate 200 discharged from the deposition chamber 20 is not in contact with another object or the protective film (before being wound around the coiler 40). 300 is preferably applied.

To this end, the outlet of the deposition chamber 20 is formed such that the catalyst substrate 200 is discharged along the tangent of the deposition drum 27. Accordingly, the graphene forming surface of the catalyst substrate 200 may be minimized from being damaged due to contact with a roll or other object.

While specific embodiments of the invention have been described and illustrated above, it is to be understood that the invention is not limited to the described embodiments, and that various modifications and changes can be made without departing from the spirit and scope of the invention. It is obvious to those who have. For example, the form of the catalyst substrate presented in the present invention does not depart from the spirit of the present invention even if it is replaced by a wire rod, a rod, a tube. Therefore, such modifications or variations are not to be understood individually from the technical spirit or viewpoint of the present invention, and the modified embodiments shall belong to the claims of the present invention.

Continuous graphene manufacturing apparatus according to the present invention, each configuration is made of a continuous type interlocking with each other to achieve a compact structure and easy design for vacuum and exhaust, forming a graphene by going through a step forming process before the deposition process Prior to this, nano-steps are formed on the entire surface of the catalyst substrate, so that physical adsorption of the precursor gas can be easily performed, thereby obtaining uniform nucleation and shortening deposition time.

Claims (24)

1. In the graphene manufacturing apparatus for synthesizing the graphene continuously in the deposition chamber for supplying the carbon precursor to the catalyst substrate,

   An uncoiler for continuously supplying the catalyst substrate;

   A coiler that receives the catalyst substrate continuously from the deposition chamber; And

   Continuous graphene manufacturing apparatus comprising a shell containing the deposition chamber, the uncoiler and the coiler.
2. The method of claim 1,

   A first heating line for maintaining annealing temperature above the recrystallization temperature of the catalyst substrate and a first gas supply line for forming a gas atmosphere having a molecular weight of at least carbon atoms, such that a step structure is formed on the surface of the catalyst substrate; Continuous graphene manufacturing apparatus characterized in that it further comprises a step forming chamber.
3. The method of claim 1,

   In the deposition chamber, a second heating wire for maintaining a temperature of 600 ~ 1100 ℃, a second shielding material to surround the heat or magnetic field of the second heating wire and a second gas supply line for supplying a carbon precursor to the catalyst substrate Continuous graphene manufacturing apparatus characterized in that it is provided.
4. The method of claim 3,

   The second heating wire is an induction heating coil, the second shielding material is a continuous graphene manufacturing apparatus, characterized in that made of any one or more of silicon steel sheet, amorphous film laminated material, iron-based soft powder powder sintered material.
5. The method of claim 3,

   The second heating wire is an electrical resistance heating wire, the second shielding material is made of any one of stainless steel sheet, titanium plate, heat-resistant tempered glass, quartz, pyrolytic boron nitride, pyrolytic graphite, gold mica, silicon carbide, alumina, magnesia, zirconia Continuous graphene manufacturing apparatus, characterized in that or a mixture thereof.
6. The method of claim 1,

   A housing chamber accommodating the uncoiler and the coiler and formed adjacent to the deposition chamber;

   The rochelle forms a sealed space surrounding the receiving chamber and the deposition chamber,

   The rochelle is made of a double wall structure, continuous graphene manufacturing apparatus, characterized in that the double wall is filled with a vacuum or insulation.
7. The method of claim 3,

   In the deposition chamber, a continuous graphene manufacturing apparatus, characterized in that the cylindrical deposition drum is formed in which the catalyst substrate is in close contact.
8. The method of claim 7, wherein

   Inside the deposition chamber, continuous graphene manufacturing apparatus characterized in that the deposition roll is formed to guide the catalyst substrate in close contact with the deposition drum in a predetermined section.
9. The method of claim 1,

   Inlet and outlet of the deposition chamber is formed with a speed sensor for detecting the moving speed of the catalyst substrate,

   Continuous graphene manufacturing apparatus characterized in that the rotational speed of the coiler and the uncoiler is controlled by the speed sensor.
10. The method according to any one of claims 1 to 9,

    A reorganization gas tank in which reorganization gas supplied into the deposition chamber is stored;

    A carbon precursor tank in which a carbon precursor supplied into the deposition chamber is stored; And

    Further comprising a hydrogen tank for storing hydrogen supplied into the deposition chamber,

    Continuous graphene manufacturing apparatus, characterized in that the supply of the reorganization gas and hydrogen is made selectively.
11. The method of claim 10,

    And a recovery device for recovering the gas exhausted from the deposition chamber to the restructured gas tank, the carbon precursor tank, and the hydrogen tank, respectively.
12. The method according to any one of claims 1 to 9,

    Continuous graphene manufacturing apparatus, characterized in that the break detection sensor for detecting the break of the catalyst substrate is formed inside the deposition chamber.
13. The method according to any one of claims 1 to 9,

    At least one of the inlet and outlet of the deposition chamber, continuous graphene manufacturing apparatus, characterized in that the buffer portion for releasing the tensile force applied to the catalyst substrate in the deposition chamber is formed.
14. The method according to any one of claims 1 to 9,

    The catalyst substrate is a continuous graphene manufacturing apparatus, characterized in that any one or more of the transition element or group 13 to 15 elements having a hydrogen solubility in the range of 600 ~ 1060 or carbide.
15. The method of claim 10,

    The reorganization gas, nitrogen, neon, argon, krypton, xenon, carbon monoxide, carbon dioxide, nitrogen oxides, ammonia, water vapor is any one of the continuous graphene production apparatus.
16. The method of claim 1,

    The catalyst substrate is overlapped in two layers,

    First gas supply for supplying a step gas to both sides of the catalyst substrate to form a first heating wire and a gas atmosphere having a molecular weight of at least carbon atoms to maintain the annealing temperature or more of the recrystallization temperature of the catalyst substrate overlapped in two layers A line is provided, comprising a step forming chamber to form a step structure on the catalyst substrate,

    The deposition chamber includes a second heating line for maintaining a temperature of 600 to 1100 ° C. and a second gas supply line for supplying hydrocarbon gas to both surfaces of the catalyst substrate through the step forming chamber. Graphene Manufacturing Equipment.
17. The method of claim 16,

    The first gas supply line and the second gas supply line is a continuous graphene manufacturing apparatus, characterized in that disposed on both sides of the catalyst substrate overlapped in two layers.
18. The method of claim 16,

    Continuous catalytic production apparatus, characterized in that the catalyst substrate is transferred in the longitudinal direction in the step forming chamber and the deposition chamber.
19. The method of claim 13,

    The buffer unit includes a press roll formed at the outlet of the deposition chamber,

    The pressure roll is a continuous graphene manufacturing apparatus, characterized in that formed to rotate at no load while pressing the catalyst substrate.
20. The method of claim 13,

    The buffer unit includes a pressure roll formed at the inlet or outlet of the deposition chamber,

    The pressing roll is a continuous graphene manufacturing apparatus, characterized in that the step is formed at both ends to serve as a guide for contacting only a part of both ends of the catalyst substrate or supporting only both sides.
21. The method of claim 13,

    The buffer unit includes a driving roll formed at each of the inlet and outlet of the deposition chamber,

    The driving roll is a continuous graphene manufacturing apparatus, characterized in that the rotating in contact with the catalyst substrate and the speed is synchronized with each other.
22. The method of claim 4, wherein

    And a spacing between the catalyst substrate and the induction heating coil is within 10 mm, and the induction heating frequency is 10 kHz or more.
23. The method according to any one of claims 1 to 9,

    The outer surface of the catalyst substrate is discharged from the deposition chamber is continuous graphene manufacturing apparatus, characterized in that before being wound on the coiler, do not contact with other objects or a protective film is applied.
24. The method of claim 7, wherein

    The outlet of the deposition chamber, the continuous graphene manufacturing apparatus, characterized in that the catalyst substrate is formed to be discharged along the tangent of the deposition drum.

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