KR20240114104A - 3-dimensional graphene nano-structure coating euipment - Google Patents

Abstract

The present invention relates to a three-dimensional graphene nanostructure coating device, which can stably generate a uniform, high-density, large-area plasma, thereby producing a three-dimensional graphene nanostructure with significantly improved electrical and mechanical properties. , It relates to a three-dimensional graphene nanostructure coating device that can be synthesized and coated in a single chamber, greatly improving process simplification and economic efficiency, a coating method using the same, and a three-dimensional graphene nanostructure manufactured through the same.

Description

3-dimensional graphene nano-structure coating device {3-dimensional graphene nano-structure coating euipment}

The present invention relates to a three-dimensional graphene nanostructure coating device, which can stably generate a uniform, high-density, large-area plasma, thereby producing a three-dimensional graphene nanostructure with significantly improved electrical and mechanical properties. , It relates to a three-dimensional graphene nanostructure coating device that can be synthesized and coated in a single chamber, greatly improving process simplification and economic efficiency, a coating method using the same, and a three-dimensional graphene nanostructure manufactured through the same.

Graphene is a material that is 200 times stronger than iron and conducts electricity up to 100 times better than copper, and is very thin at 0.33 nm in thickness, so it can be applied to a variety of fields. In addition, it has more than twice the thermal conductivity of single crystal silicon, which boasts the best thermal conductivity, and is recognized as a groundbreaking material that will lead the 4th industrial revolution with excellent transparency and airtightness. Accordingly, various studies are being conducted to commercialize graphene, but the research using graphene introduced to date has limitations in commercialization due to the following research.

First, the biggest problem in using graphene, which has excellent electrical, chemical, and mechanical properties, is to economically expand high-quality graphene to a large area. In general, it is very efficient to use the roll-to-roll method for large-area base materials, especially flexible OLED thin film processing or plasma treatment of functional fabrics. Since this roll-to-roll method is processed by scanning from one end of the base material to the other end, it requires a plasma source large enough to cover the entire base material. However, in the case of a microwave plasma source according to the prior art, The length or diameter is limited to around the wavelength of the microwave, so there is a limit to processing base materials over a certain size.

As part of an effort to overcome this problem, research using ECR resonance (Electron Cyclotron Resonance) was introduced, but since ECR plasma is close to the electromagnetic wave incident window, high-energy electrons near the ECR resonance area frequently collide with the electromagnetic wave incident window. This had the problem of damaging the electromagnetic wave incident window and impairing the durability of the plasma source. In addition, the plasma source using electromagnetic waves, which is formed in an oval track shape, has an electromagnetic wave incident window and a permanent magnet placed close to the ECR plasma, so it is necessary to prevent damage due to deterioration phenomenon caused by ECR plasma, and for this purpose, the electromagnetic wave incident window and permanent magnet are placed close to the ECR plasma. An efficient cooling structure for the incident window and the permanent magnet is required, but there has been no improvement to date due to the difficulty of research and development.

Second, even if it is assumed that all of the above-mentioned problems can be overcome and large-area coating technology of high-quality graphene using plasma is possible, there are problems that require simplification of the process and optimization of design conditions to commercialize it.

In other words, even if conventional graphene coating technology is combined with plasma technology, a complex synthesis process and thin film coating process through transfer of multiple chambers are essential. The additional installation and operation of a plasma chamber with a volume corresponding to large-area graphene, and the accompanying high temperature and high pressure conditions, are obstacles to commercialization, and it is also an obstacle to the commercialization of high-density three-dimensional graphene nanostructures in a stable and stable manner. Because the design technology that enables large-area synthesis and coating is a technology that requires a high level of difficulty that cannot be borrowed from the manufacturing process of other materials, the process cost and time are high while coating high-density/high-quality/large-area graphene. There are still limitations in shortening .

Accordingly, the three-dimensional graphene nanostructure coating device is capable of generating a stable, uniform, high-density, large-area plasma, thereby manufacturing a three-dimensional graphene nanostructure with significantly improved electrical and mechanical properties, The invention relates to an optimized three-dimensional graphene nanostructure coating device that can be synthesized and coated in a single chamber, greatly improving process simplification and economic efficiency, a coating method using the same, and a three-dimensional graphene nanostructure manufactured through the same. Completed.

Republic of Korea registered patent 1797182 (2017.11.07)　

The present invention was created to overcome the above-mentioned problems, and the problem to be solved by the present invention is to provide high-quality three-dimensional graphene so that the inherent properties of graphene, which has excellent electrical, chemical, and mechanical properties, can be utilized to the maximum. The aim is to provide a three-dimensional graphene nanostructure coating device that can manufacture nanostructures at high density/large area.

In addition, another problem that the present invention aims to solve is to use ECR resonance (Electron Cyclotron Resonance) to coat large-area three-dimensional graphene nanostructures, and to provide a three-dimensional graphene nanostructure coating device that is economically efficient and durable. It is provided.

In addition, another problem that the present invention aims to solve is to facilitate and simplify the manufacturing process by simultaneously performing plasma pretreatment, transfer, synthesis, coating, and recovery in a single chamber. This allows for economic efficiency and simplification of the manufacturing process. The aim is to provide a 3D graphene nanostructure coating device that can improve all usability, a 3D graphene nanostructure coating method using the same, and a 3D graphene nanostructure manufactured through the same.

The present invention is a coating device capable of coating a large area of a three-dimensional graphene nanostructure on a metal thin film in order to solve the above-mentioned problems, comprising: a vacuum process chamber including a roll-to-roll unit for transporting and recovering the metal thin film; A three-dimensional graphene nanostructure coating device is provided, including a plasma source unit coupled to one end of a vacuum process chamber, wherein three-dimensional graphene nanostructure synthesis and coating are performed in the vacuum process chamber.

In addition, according to one embodiment of the present invention, the transfer of the metal thin film, hydrogen plasma pretreatment, synthesis and coating of the three-dimensional graphene nanostructure, and recovery of the metal thin film can be performed simultaneously in one vacuum process chamber. there is.

Additionally, the plasma source unit may include an annular or oval-shaped central waveguide including a plurality of slots on an inner surface; Electromagnetic wave transmission means for transmitting electromagnetic waves to the central waveguide; an electromagnetic wave supply unit that transmits electromagnetic waves to the electromagnetic wave transmission means; and a plasma chamber located on an outlet side of the slot to seal the inside of the central waveguide and having an electromagnetic wave incident window through which electromagnetic waves introduced through the slot can be radiated to the outside.

Additionally, the vacuum process chamber may be characterized in that a reaction gas is introduced into the vacuum process chamber, and the reaction gas has a flow rate ratio of hydrogen and methane gas of 1:0.1 to 1.

Additionally, the vacuum process chamber may further include a planar heater.

Additionally, the roll-to-roll part may be characterized as including a first roll part and a second roll part.

In addition, the electromagnetic wave transmitting means is a tuner installed on one side of the central waveguide and transmitting electromagnetic waves from the electromagnetic wave supply unit into the central waveguide, and between the central waveguide and the tuner, both ends are connected to the central waveguide and the tuner, respectively. A directly connected transmission waveguide is installed, so that electromagnetic waves from the electromagnetic wave supply unit are transmitted to the center waveguide through the transmission waveguide, and the waveguide of the electromagnetic wave supply unit is arranged to form a tangent to one side of the center waveguide, and the electromagnetic wave The transmission means is a rod-shaped conductor that penetrates the center waveguide and the waveguide of the electromagnetic wave supply unit perpendicular to the tangent line, and the center waveguide includes a first straight right-angle waveguide and a second straight right-angle parallel to the first straight right-angle waveguide. A waveguide, a first curved right-angle waveguide connecting the ends of the first and second straight right-angle waveguides on one side to enable electromagnetic wave communication, and a second curved right-angle waveguide connecting the ends of the first and second straight right-angle waveguides on the other side to enable electromagnetic wave communication. 2 It may be characterized as including a curved right-angle waveguide.

In addition, the straight and curved right-angle waveguides are in TE mode, one of the two sides perpendicular to the electric field in the straight and curved right-angle waveguides is erected to face inward, and the slot is located on the inner side of the straight right-angle waveguide. It can be characterized as being formed in .

In addition, the straight right-angle waveguide may be WR430, and the curved right-angle waveguide may be WR284.

In addition, the slot is a slot erected perpendicular to the electromagnetic wave circulation direction of the center waveguide, is located between the inner surface of the center waveguide and the electromagnetic wave incident window, and includes a magnet unit disposed between the slots, and the electromagnetic wave is incident. The window may be installed to seal the gap formed by the magnetic units.

In addition, the magnet units are arranged in pairs up and down parallel to the slot direction to form a toroidal magnetic field in the central waveguide, and the magnetization direction formed by the pair of magnet units is parallel to the slot direction. It can be characterized.

In addition, the magnet units are arranged in pairs to the left and right perpendicular to the slot direction, the magnetization direction formed by the pair of magnet units is perpendicular to the slot direction, and the magnetic field formed by the pair of magnet units is positioned in the slot. It can be characterized as crossing.

In addition, it includes a pair of non-penetrating vertical holes fluidly connected to the ends of the flow path and a horizontal flow path crossing the magnet unit fluidly connecting the pair of vertical holes within the lower fixing plate,

The upper fixing plate has a pair of non-penetrating vertical holes fluidly connected to one of the pair of cooling conduits of the yoke and an end of the cooling conduit of the adjacent yoke, and the pair of vertical holes in the upper fixing plate. It may be characterized by comprising a horizontal flow path across the slot connecting fluid communication.

In addition, a yoke surrounding the pair of magnet units, disposed between the slots, and including a pair of cooling passages vertically penetrating parallel to the slots within two side walls; a ring-shaped or oval-shaped upper fixing plate and a ring-shaped or oval-shaped lower fixing plate located inside the center waveguide and arranged to cover the upper and lower surfaces of the yoke along the traveling direction of the center waveguide; an inlet through which coolant is supplied to one of the pair of cooling passages through a through hole penetrating the lower fixing plate; and an outlet through which coolant is discharged from one of the pair of cooling passages through a through hole penetrating the lower fixing plate, and one or more magnet units including a yoke between the inlet and the outlet, wherein the upper fixing plate A pair of non-penetrating vertical holes fluidly connected to the ends of a pair of cooling channels formed in the two side walls of the yoke, and the magnet unit fluidly connecting the pair of vertical holes within the upper fixing plate are horizontally connected. It includes a horizontal flow path running through the lower fixed plate, a pair of non-penetrating vertical holes fluidly connected to an end of the cooling flow path of the yoke adjacent to one of the pair of cooling flow paths of the yoke, and the pair of vertical holes. It may be characterized by including a horizontal flow path crossing the slot connecting the hole to fluid communication within the lower fixing plate.

In addition, the upper or lower fixing plate has a laminated structure of a cover layer located on the outside and a flow path layer located on the inside, and the vertical hole of the upper or lower fixing plate is a through hole formed in the flow path layer, and the upper fixing plate The horizontal flow path of the plate may be characterized as a horizontal groove formed on the surface of the flow path layer facing the cover layer.

In addition, the upper or lower fixing plate has a laminated structure of a cover layer located on the outside and a flow path layer located on the inside, and the vertical hole of the upper or lower fixing plate is a through hole formed in the flow path layer, and the upper fixing plate The horizontal flow path of the plate may be characterized as a horizontal groove formed on the surface of the flow path layer facing the cover layer.

In addition, the present invention includes a first step in which the metal thin film supplied through the first roll part of the roll-to-roll part is pretreated with hydrogen plasma in a vacuum process chamber, a second step in which a three-dimensional graphene nanostructure is synthesized and coated on the metal thin film, and A method for coating a three-dimensional graphene nano structure is provided, which includes a third step of recovering the metal thin film on which the three-dimensional graphene nano structure is synthesized and coated through the second roll part of the roll-to-roll part in a vacuum process chamber.

In addition, what is the purpose of the present invention? According to this, a reaction gas containing hydrogen and methane gas is introduced into the vacuum process chamber, and the hydrogen and methane gas may be introduced at a flow rate ratio of 1:0.1 to 1.

Additionally, the vacuum process chamber may maintain a process pressure of 1 to 3 mTorr.

Additionally, the second step may be characterized as a synthesis step for 1 to 60 minutes.

In addition, the present invention provides a three-dimensional graphene nanostructure that is manufactured by coating a metal thin film and a three-dimensional graphene nanostructure according to claims 18 to 22, and has a specific capacitance of 2.0 F/cm ² or more. .

Additionally, according to one embodiment of the present invention, the pore size may be 10 to 300 nm.

According to the present invention, high-quality three-dimensional graphene can be made to maximize the inherent properties of graphene, which has excellent electrical, chemical, and mechanical properties, using a highly economical and durable three-dimensional graphene nanostructure coating device. Nanostructures can be manufactured in large areas. In addition, the three-dimensional graphene nanostructure coating device according to the present invention can facilitate and simplify the manufacturing process by simultaneously performing hydrogen plasma pretreatment, transfer, synthesis, coating, and recovery within a single chamber, thereby improving economic efficiency. Its usability in various industries can be significantly improved.

1 is a schematic diagram showing an exploded view of a three-dimensional graphene nanostructure coating device according to an embodiment of the present invention.
Figure 2 is a conceptual diagram of a three-dimensional graphene nanostructure coating device according to an embodiment of the present invention.
Figure 3 is a projection diagram showing a combined state of a three-dimensional graphene nanostructure coating device according to an embodiment of the present invention.
Figure 4 is an SEM image of a three-dimensional graphene nanostructure manufactured at different flow rates according to an embodiment of the present invention.
Figure 5 is an SEM image of a three-dimensional graphene nanostructure manufactured at different synthesis times according to an embodiment of the present invention.
Figure 6 shows the Raman measurement results of a three-dimensional graphene nanostructure manufactured at different synthesis times according to an embodiment of the present invention.
Figure 7 shows the capacitance measurement results of a three-dimensional graphene nanostructure manufactured by varying the flow rate according to an embodiment of the present invention.
Figure 8 is an image showing the results of a plasma generation test for each pressure zone in the 3D graphene synthesis process according to an embodiment of the present invention.
Figure 9 is a cross-sectional view for explaining the configuration of a plasma source unit using a resonance waveguide according to an embodiment of the present invention.
FIG. 10 is a cross-sectional view taken along line A-A' of FIG. 1.
FIG. 11 is a perspective view showing the central waveguide and plasma chamber shown in FIG. 1.
FIG. 12 is a diagram showing the appearance of the straight section yoke shown in FIG. 1.
FIG. 13 is a diagram for explaining the magnet unit shown in FIG. 1.
Figure 14 is a cross-sectional view showing the transmission of electromagnetic waves and the generation of plasma in the plasma source unit by a resonance waveguide according to an embodiment of the present invention.
Figure 15 is a diagram showing the results of a three-dimensional magnetic field computer simulation of an embodiment of the magnet unit arrangement.
Figure 16 is a diagram showing the formation of the 875G isoline at the center of a pair of magnet units spaced apart in the slot direction and the formation of the 875G isoline between slots in an embodiment of the magnet unit arrangement.
Figure 17 is a diagram showing the radial profiles of the magnetic field at the slot location and a pair of upper and lower permanent magnet locations in an embodiment of the permanent magnet arrangement.
Figure 18 is a diagram showing the results of 3D magnetic field computer simulation of a comparative example for the arrangement of magnet units.
Figure 19 is a diagram showing the formation of the 875G isoline at the center of a pair of magnet units spaced apart in the slot direction and the formation of the 875G isoline between slots in a comparative example of magnet unit arrangement.
Figure 20 is a diagram showing the radial profiles of the magnetic field at the slot position and a pair of upper and lower magnet unit positions in a comparative example of magnet unit arrangement.
FIG. 21 is a diagram illustrating an example of an electromagnetic wave transmission means of a plasma source unit using a resonance waveguide according to an embodiment of the present invention.
Figure 22 is a partially enlarged cross-sectional view for explaining the cooling structure at the slot position of the plasma source unit by the resonance waveguide according to an embodiment of the present invention.
Figure 23 is a partially enlarged cross-sectional view to explain the cooling structure in the curved section of the plasma source unit by the resonance waveguide according to an embodiment of the present invention.
Figure 24 is a diagram for explaining a plasma source unit using a resonance waveguide according to another embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. The present invention may be implemented in many different forms and is not limited to the embodiments described herein.

As mentioned above, there has been a continued demand to utilize the excellent properties of graphene in various industries recently, but due to issues such as difficulty in research and development, process cost and design optimization, stability and large area, 3D nanotechnology using graphene has been developed. Research on structure synthesis and coating devices for metal thin films is urgently needed.

Accordingly, the present invention is a coating device capable of coating a large area of a three-dimensional graphene nanostructure on a metal thin film, comprising a vacuum process chamber including a roll-to-roll part for transporting and recovering the metal thin film, and coupled to one end of the vacuum process chamber. A solution to the above-described problem was sought by providing a 3D graphene nanostructure coating device that includes a plasma source unit and performs 3D graphene nanostructure synthesis and coating in the vacuum process chamber.

Through this, it is possible to generate stable, uniform, high-density, large-area plasma, making it possible to manufacture three-dimensional graphene nanostructures with significantly improved electrical and mechanical properties, and preprocessing, transfer, synthesis, and coating in a single chamber. This can greatly improve process simplification and economic efficiency.

The present invention will be described in detail below with reference to the drawings.

The three-dimensional graphene nanostructure coating device according to the present invention includes a vacuum process chamber 300 including a plasma source unit 100 and a roll-to-roll unit 200 for transporting and recovering a metal thin film.

Figure 1 is a schematic diagram showing an exploded view of a three-dimensional graphene nanostructure coating device according to an embodiment of the present invention, where one end of the vacuum process chamber 300 is coupled to the plasma source unit 100, and the The other end of the vacuum process chamber 300 is coupled to the roll-to-roll unit 200, and three-dimensional graphene nanostructure synthesis and coating are performed on the metal thin film by plasma generated from the plasma source unit 100.

A typical graphene synthesis device essentially consists of a roller for supplying metal members to a synthesis unit for graphene synthesis, a graphene synthesis unit, and a roller for graphene recovery, and these are separated and placed vertically or horizontally in multiple chambers. The process proceeds. In addition, hydrogen plasma pretreatment can be performed to obtain high-quality graphene, but in this case, hydrogen plasma equipment must be added. In this case, in order to coat large-area graphene, not only each device but also the hydrogen plasma equipment must be used to cover a large area. It has to be designed with a volume that can accommodate this, which is disadvantageous in terms of process operation, and it is difficult to synthesize high-density graphene because it is difficult to supply stable and uniform plasma. Furthermore, there is a problem in that uniformity of mechanical/electrical properties cannot be guaranteed even in the manufacture of large-area graphene as desired.

Accordingly, the present invention enables hydrogen plasma pretreatment for synthesis and coating of graphene, transport and recovery of metal thin films, and synthesis and coating of graphene in a single chamber without a separate chamber, as shown in the conceptual diagram of FIG. 2. By overcoming the problem and at the same time greatly reducing the weight and volume of the device, its usability can be greatly improved.

More specifically, referring to FIG. 3, the three-dimensional graphene nanostructure coating device according to an embodiment of the present invention is a vacuum process chamber when a metal thin film is transferred through the first roll unit 210 in the vacuum process chamber 300. (300) Pretreatment may be performed by hydrogen plasma generated from the lower plasma source unit 100. According to a preferred embodiment of the present invention, the metal thin film is mounted in roll form on the first roll unit 210 and can be transported by a rewinder connected to a servo motor.

The pretreatment using hydrogen plasma can be used to remove impurities on the metal thin film on which graphene will be synthesized, to make the structure of the metal thin film dense, and to grow the size of the structure. In this case, a partition wall may be installed to prevent movement of impurities removed by the plasma process. At this time, as shown in FIG. 3, the plasma source unit 100 is located below the vacuum process chamber 300 and is not located in a separate chamber.

Thereafter, in the present invention, graphene can be synthesized and coated on the surface of the metal thin film pretreated in the vacuum process chamber 300 at the same time. As a method for synthesizing graphene, any chemical vapor deposition method commonly used in the art can be used without limitation, for example, thermal chemical vapor deposition (T-CVD). , rapid thermal chemical vapor deposition (RTCVD), plasma enhanced chemical vapor deposition (PECVD), inductively coupled plasma enhanced chemical vapor deposition (ICPCVD), organic metal Chemical vapor deposition (MOCVD), low pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition (APCVD), or laser heating can be used. It is not limited.

The synthesis and coating of the graphene is performed by injecting a reaction gas containing a carbon source through a gas nozzle (not shown) in the vacuum process chamber 300, and applying chemical vapor deposition to the surface of the metal thin film in the graphene synthesis unit. Graphene may be synthesized and coated.

The reaction gas containing the carbon source may exist only with the carbon source, or the carbon source and an inert gas such as helium, argon, etc. may exist together. Additionally, the reaction gas containing the carbon source may contain hydrogen in addition to the carbon source. Hydrogen can be used to control gas phase reactions by keeping the surface of the substrate clean. The carbon source may include carbon sources such as carbon monoxide, carbon dioxide, methane, ethane, ethylene, ethanol, acetylene, propane, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene, toluene, polymer, etc. However, it is not limited to this.

At this time, while supplying the reaction gas containing the carbon source to the vacuum process chamber 300 in a gaseous state, the carbon source is heat-treated by the planar heater 310 included in the vacuum process chamber 300 capable of controlling the temperature. Graphene is synthesized as the carbon components present in combine to form a hexagonal plate-shaped structure on the surface of the metal thin film. By the heat treatment, the reaction temperature can be maintained at about 300°C to about 2000°C, and the graphene produced by the above-mentioned method may be single-layer graphene or multi-layer graphene.

At this time, the metal thin film may be a known conventional metal thin film suitable for coating a three-dimensional graphene nanostructure suitable for the purpose of the present invention. For example, it can serve as a support for graphene and at the same time contribute to the growth of graphene. It acts as a catalyst, and a flexible copper substrate is generally used, or Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Ir, Si, Ta, Ti, W At least one material selected from the group consisting of , Pd, V, and Zr may be used, or an alloy thereof may be used, or a multi-layered metal thin film manufactured from these may be used, but is not limited thereto.

Meanwhile, in synthesizing and coating graphene on such a metal thin film, the present invention can form graphene in the form of a high-quality/high-density/large-area three-dimensional nanostructure, which is explained in more detail with reference to FIGS. 4 to 7. do.

The present invention can control the uniformity of the three-dimensional graphene nanostructure by controlling the flow rate ratio of hydrogen and methane gas included in the reaction gas flowing into the vacuum process chamber 300.

At this time, the flow rate ratio of the hydrogen and methane gas may preferably be 1:0.1 to 1, and more preferably, the flow rate ratio may be 1:0.3 to 0.8 at a process pressure of 1 to 3 mTorr. At this time, if the flow rate ratio of hydrogen and methane gas included in the reaction gas flowing into the vacuum process chamber 300 is less than 1:0.1, substrate deterioration occurs due to an increase in plasma temperature, and the three-dimensional graphene nanostructure is not sufficiently synthesized. Also, if the flow rate ratio of hydrogen and methane gas included in the reaction gas flowing into the vacuum process chamber 300 exceeds 1: 1, the synthesized three-dimensional graphene nanostructure may have an irregular structure. there is. That is, referring to FIG. 4, when the numerical range of the preferred flow rate ratio according to the present invention is satisfied (center image of FIG. 4), it can be seen that the upper edge of the three-dimensional graphene nanostructure exhibits an orderly and uniform structure. However, in the present invention, If the lower and upper limits of the numerical range of the desirable flow ratio are below (left image of Figure 4) or exceeded (right image of Figure 4), the three-dimensional graphene nanostructure is not completely synthesized, or even if synthesized, the upper edge of the structure is irregular. You can see that it appears.

In addition, the present invention can control the pore size of the three-dimensional graphene nanostructure to 10 to 300 nm by controlling the synthesis time in the vacuum process chamber 300.

At this time, the time for synthesizing the graphene may preferably be 1 to 60 minutes. More specifically, referring to FIG. 5, the three-dimensional graphene nanostructure synthesized by keeping the flow rate of incoming hydrogen and methane constant and varying the time at 7, 15, 30, and 60 minutes, respectively, was measured at the same magnification. FE-SEM images show that the pore size between the three-dimensional structures increases as the synthesis time increases.

In addition, the present invention can control the electrical properties and capacitance of the three-dimensional graphene nanostructure by simultaneously controlling the synthesis time and flow rate within the vacuum process chamber 300. More specifically, referring to FIG. 6, the Raman measurement results and relative intensities of major bands according to synthesis time can be seen. Also, referring to FIG. 7, the characteristics of the capacitor according to flow rate can be confirmed. Through this, it can be seen that the present invention can manufacture high-quality three-dimensional graphene nanostructures with a specific capacitance of 2.0 F/cm ² or more in a large area.

Next, the plasma source unit 100 according to the present invention will be described in detail.

FIG. 9 is a cross-sectional view for explaining the configuration of the plasma source unit 100 using a resonance waveguide according to an embodiment of the present invention, FIG. 10 is a cross-sectional view taken along line A-A' in FIG. 91, and FIG. 11 is in FIG. 9. This is a perspective view showing the central waveguide and plasma chamber shown.

9 to 11, the resonant waveguide according to an embodiment of the present invention includes a central waveguide 110, an electromagnetic wave transmission means 120, an electromagnetic wave supply unit 130, a plasma chamber 140, and an electric field control means ( 150) may be included.

The central waveguide 110 is provided in the form of a track to transmit electromagnetic waves clockwise or counterclockwise, and is arranged to surround the circumference of the plasma chamber 140 to transmit electromagnetic waves through the electromagnetic wave transmission means 120. It can be evenly incident on the inside of the plasma chamber 140. For example, the central waveguide 110 may be provided in a circular or oval shape. The center waveguide 110 is a right angle waveguide.

Specifically, the center waveguide 110 may include a first straight right angle waveguide 111, a second straight right angle waveguide 112, a first curved right angle waveguide 113, and a second curved right angle waveguide 114. there is.

The first straight right angle waveguide 111 is a waveguide extending linearly in one direction of the central waveguide 110.

The second straight right angle waveguide 112 is a waveguide parallel to the first straight right angle waveguide 111 in the center waveguide 110.

The first curved right-angle waveguide 113 is connected to one side of the center waveguide 110, that is, in the direction of one end of the first straight right-angle waveguide 111 and the second straight right-angle waveguide 112. The ends of the second straight right angle waveguide 112 are connected to enable electromagnetic wave communication.

The second curved right-angle waveguide 114 is connected to the other side of the center waveguide 110, that is, in the direction of the other end of the first straight right-angle waveguide 111 and the second straight right-angle waveguide 112. The ends of the second straight right angle waveguide 112 are connected to enable electromagnetic wave communication.

In this structure of the center waveguide 110, the first and second straight right angle waveguides 111 and 112 and the first and second curved right angle waveguides 113 and 114 are in TE mode, and the center waveguide 110 is in the first mode. One of the two sides perpendicular to the electric field in the first and second straight right-angle waveguides (111, 112) and the first and second curved right-angle waveguides (113, 114) is inside the annular or elliptical shape of the center waveguide (110). It can be placed facing upright. At this time, among the two erected sides of each right angle waveguide (111, 112, 113, 114), the side facing the annular or elliptical inner side of the center waveguide 110 is the inner side of the center waveguide 110 and the side of the center waveguide 110 is the inner side of the center waveguide 110. The annular or elliptical outward facing surface is the outer surface of the central waveguide 110.

In one embodiment, the first and second straight right angle waveguides 111 and 112 may be configured as WR430 waveguides, and the first and second curved right angle waveguides 113 and 114 may be configured as WR284 waveguides.

Meanwhile, the central waveguide 110 may include a plurality of slots 115. The slot 115 may be provided to radiate electromagnetic waves within the central waveguide 110 to the outside. For example, a plurality of slots 115 may be provided at regular intervals on the inner surfaces of the first straight right angle waveguide 111 and the second straight right angle waveguide 112. At this time, the slot 115 may be formed to stand perpendicular to the electromagnetic wave circulation direction of the central waveguide 110.

Here, the area where the slots 115 of the first straight right angle waveguide 111 and the second straight right angle waveguide 112 are formed form a pair of straight sections S1 and S2 of the center waveguide 110. and the remaining areas of the first straight right angle waveguide 111 and the second straight right angle waveguide 112 adjacent to the first curved right angle waveguide 113 and the second curved right angle waveguide 114. The first curved right-angle waveguide 113 and the second curved right-angle waveguide 114 may form a pair of curved sections C1 and C2 of the center waveguide 110.

In addition, the length of the straight sections (S1, S2) may be formed as n λ _g /2. (Here, λ _g refers to the size of the guided wavelength within the waveguide, and n is a natural number (1 ,2,3..n)) Therefore, the electric field from the two opposing slots 115 undergoes constructive interference near the center of the plasma chamber 140, thereby further increasing the size of the electric field.

The electromagnetic wave transmission means 120 transmits electromagnetic waves to the central waveguide 110.

FIG. 21 is a diagram illustrating an example of an electromagnetic wave transmission means of the plasma source unit 100 using a resonance waveguide according to an embodiment of the present invention.

Referring to FIG. 21 , as an example, the electromagnetic wave transmission means 120 may be a rod-shaped conductor 121. The rod-shaped conductor 121 may be disposed perpendicular to a tangent line on one side of the central waveguide 110, penetrating the waveguide 131 and the central waveguide 110 of the electromagnetic wave supply unit 130, which will be described later. .

Referring to FIG. 9, as another example, the electromagnetic wave transmitting means 120 is installed on one side of the central waveguide 110, and the tuner 122 transmits the electromagnetic waves of the electromagnetic wave supply unit 130 into the central waveguide 110. ) can be. The tuner 122 controls the intensity of the incident wave and the reflected wave of the electromagnetic wave transmitted from the electromagnetic wave supply unit 130 to induce impedance matching so that the electric field induced by the electromagnetic wave is maximized within the plasma chamber 140. You can.

Referring to FIG. 9, as another example, the electromagnetic wave transmission means 120 is between the tuner 122 and the central waveguide 110, and both ends are directly connected to the central waveguide 110 and the tuner 122, respectively. It may further include a transmission waveguide 123. Electromagnetic waves from the electromagnetic wave supply unit 130 may be transmitted to the central waveguide 110 through the transmission waveguide 123.

In this case, as the length or size of the track-shaped plasma source unit 100 increases, sufficient power required can be applied. That is, compared to the case of the rod-shaped conductor 121, in a structure in which electromagnetic waves are transmitted directly to the central waveguide 110 through the transmission waveguide 123, the high output power required by the track-shaped plasma source unit 100 can be easily conveyed.

The electromagnetic wave supply unit 130 transmits electromagnetic waves to the electromagnetic wave transmission means 120. For example, the electromagnetic wave supply unit 130 may include a magnetron (not shown) and a waveguide 131 that transmits electromagnetic waves oscillated from the magnetron.

The plasma chamber 140 is disposed along the inner circumference of the central waveguide 110 and is located inside the central waveguide 110, and electromagnetic waves can be incident therein from the central waveguide 110. For example, the plasma chamber 140 may be provided in an annular or oval shape.

To allow electromagnetic waves to enter the plasma chamber 140, the plasma chamber 140 may be provided with an electromagnetic wave incident window 141. The electromagnetic wave incident window 141 is disposed to face the plurality of slots 115 of the central waveguide 110. That is, the electromagnetic wave incident window 141 is located on the exit side of the plurality of slots 115 to seal the interior of the central waveguide 110, and the electromagnetic wave introduced through the plurality of slots 115 enters the plurality of slots 115. It may be provided to radiate to the outside, that is, to the inside of the plasma chamber 140. The electromagnetic wave incident window 141 may be provided in plurality, and may be arranged to face the inner surface of each first straight right-angled waveguide 111 and the inner surface of the second straight right-angled waveguide 112.

The electric field control means 150 is disposed on the other side of the central waveguide 110, and can adjust the distribution of the electric field in the plasma chamber 140 according to the position of the plunger 151 fastened to the other side of the central waveguide 110. . That is, when the plunger 151 is pushed inward at the optimal position of the plunger 151, the electric field becomes stronger on the right side of the plasma chamber 140, and conversely, when the plunger 151 is pushed inward at the optimal position of the plunger 151, the electric field becomes stronger. If subtracted from , the electric field may become stronger on the left side of the plasma chamber 140. Accordingly, the electric field control means 150 can easily adjust and control the uniformity of plasma by changing the magnetic field distribution within the plasma chamber 140 through the position of the plunger 151 during actual plasma operation.

FIG. 12 is a diagram showing the straight section yoke shown in FIG. 9, and FIG. 13 is a diagram explaining the permanent magnet shown in FIG. 1.

Meanwhile, the plasma source unit 100 using a resonance waveguide according to an embodiment of the present invention may further include a magnet unit 170.

The magnet unit 170 refers to a permanent magnet and can form a magnetic field toward the inside of the plasma chamber 140. The magnet unit 170 is located between the inner surface of the central waveguide 110 and the electromagnetic wave incident window 141 and is disposed between the slots 115. In detail, the magnet unit 170 is arranged along the electromagnetic wave circulation direction of the center waveguide 110 between the plasma chamber 140 and the inner surface of the center waveguide 110, and the first straight right angle waveguide 111 and the Arranged in the straight sections (S1, S2) by the second straight right-angle waveguide 112 and the curved sections (C1, C2) by the first curved right-angle waveguide 113 and the second curved right-angle waveguide 114. It can be. At this time, the electromagnetic wave incident window 141 is installed to seal the gap formed by the magnet units 170. That is, it is installed to seal the gap between the magnet units 170 opposing the slot 115. This magnet unit 170 serves to confine electrons to prevent them from escaping within the plasma chamber 140.

The magnet units 170 are arranged up and down parallel to the direction of the slot 115 as shown in FIG. 10 to form a toroidal magnetic field in the central waveguide 110, so that the magnetization direction formed by the pair of magnet units 170 may be parallel to the direction of the slot 115. According to the magnetization direction structure of the pair of magnet units 170, the magnetic field direction within the plasma chamber 140 may be formed parallel to the direction of the slot 115.

The magnet unit 170 may be fixed by yokes 180a and 180b. The yokes 180a and 180b may be fixed between the central waveguide 110 and the electromagnetic wave incident window 141 so that the magnetization direction of the pair of magnet units 170 is parallel to the direction of the slot 115. Referring to FIG. 12, the yokes (180a, 180b) may be formed to have a pair of magnet arrangement grooves 183 disposed at regular intervals above and below the body, and the pair of magnet arrangement grooves 183 ) It may be configured to accommodate a pair of magnet units 170, respectively. These yokes (180a, 180b) may be made of iron, and serve as a magnetic field yoke to limit the magnetic force lines generated by the pair of magnet units 170 to the inside of the yokes (180a, 180b), and to the plasma chamber 140. It can play a role in forming a larger magnetic field inside.

Meanwhile, the yokes 180a and 180b can be divided into a straight section yoke 180a and a curved section yoke 180b. The straight section yoke 180a may be a yoke disposed between slots 115 within the straight sections S1 and S2, and the curved section yoke 180b may be located outside the area where the slots 115 are disposed, that is, the above. It may be a yoke disposed in the curved sections (C1, C2).

The horizontal width of the first surface 181 of the straight section yoke 180a may have a width corresponding to the width between the slots 115, and the second surface opposite to the first surface 181 may have a width corresponding to the width between the slots 115. The width of the surface 182 is narrower than the width of the first surface 181, and each side 182 on the left and right sides of the yoke 180a connecting the first surface 181 and the second surface 182 ) can be formed tapered. In this structure of the yoke 180a, the pair of magnet placement grooves 183 may be formed by being recessed from the first surface 181, and the first surface 181 is the inner surface of the central waveguide 110. That is, the first straight right-angle waveguide 111 and the second straight right-angle waveguide 112 may be in close contact with each inner surface, and the second surface 182 may be in close contact with the electromagnetic wave incident window 141. According to the shape and arrangement structure of the yoke 180a, the gap between the yokes 180a is opposite to the slot 115 to form a path that guides the electromagnetic wave radiating from the slot 115 toward the electromagnetic wave incident window 141. can do.

The path forms a path through which electromagnetic waves transmitted from the slot 115 are transmitted between two adjacent magnet units 170 with the slot 115 in between, and the path has a narrow inlet and an expanded outlet shape. The horizontal cross section is formed in a trapezoidal shape. Accordingly, the path may expand as the electromagnetic wave from the slot 115 passes through the path and enter the inside of the central waveguide 110.

The curved section yoke 180b may be formed in a shape corresponding to the curved sections C1 and C2, for example, a U shape, and both ends have a gradient angle equal to the side surface of the straight section yoke 180a. may be formed, and a pair of magnet arrangement grooves 183 disposed above and below the body of the curved section yoke 180b may be arranged along the U-shape.

Here, the straight section yokes (180a) and the curved section yokes (180b) cover the upper part of the yokes (180a, 180b) and form the yokes (180a, 180b) between the central waveguide 110 and the plasma chamber 140. They may be fixed through an upper fixing plate 161 covering the upper part of the yokes 180a and a lower fixing plate 162 covering the lower part of the yokes 180a and 180b between the central waveguide 110 and the plasma chamber 140. For example, it may be fixed to the upper and lower parts of the yokes 180a and 180b through screw coupling.

Meanwhile, the magnet units 170 may be selected in consideration of the Curie temperature and magnetic field strength.

In one embodiment, the magnet units 170 may be N42SH neodymium magnets coated with nickel on the surface, and the surface magnetic field may be 1300 mT.

In addition, the size of the magnet units 170 in the straight sections (S1, S2) may be 30 mm to 35 mm in depth and 35 to 40 mm in height, and the size of the magnet units 170 in the curved sections (C1, C2) may be 30 mm to 30 mm in depth. It can be 35mm, height 30mm~35mm.

Here, the depth of the magnet units 170 is in the d direction in FIG. 13, and the height is in the h direction in FIG. 13.

Hereinafter, the electromagnetic wave incident process and plasma formation process of the plasma source unit 100 by the resonance waveguide according to an embodiment of the present invention will be described with reference to FIG. 14. FIG. 14 is a cross-sectional view showing transmission of electromagnetic waves and generation of plasma by the plasma source unit 100 using a resonance waveguide according to an embodiment of the present invention.

To form plasma within the plasma chamber 140, electromagnetic waves are incident into the central waveguide 110 through the electromagnetic wave supply unit 130 and the electromagnetic wave transmission means 120.

The incident electromagnetic wave moves along a track-shaped movement path according to the elliptical or annular shape of the central waveguide 110. For example, incident electromagnetic waves can move clockwise.

Electromagnetic waves moving within the center waveguide 110, that is, within the track-shaped movement path, are introduced into a plurality of slots 115 arranged in the first straight right-angle waveguide 111 and the second straight right-angle waveguide 112. Then, the electromagnetic waves are radiated into the plasma chamber 140 through the electromagnetic wave incident window 141 of the plasma chamber 140.

At this time, in the curved sections C1 and C2, hot electrons generated near the slot 115 rotate in the circumferential direction while drifting along the shape of the plasma chamber 140 by the magnetic field, and the plasma chamber ( Plasma is generated while continuously rotating along the shape of 140). As a result, the generated high-temperature electrons have a closed-circuit movement path and contribute to ionization throughout the plasma chamber 140. Due to this structure, the plasma is confined in a magnetic field and made into a closed circuit, thereby improving not only the density but also the uniformity of the plasma. It also has a huge advantage.

Hereinafter, the shape of the magnetic field and the resulting plasma will be discussed through examples and comparative examples in which the design of the size of the permanent magnets 171 and 172 in the straight sections (S1, S2) and the curved sections (C1, C2) is different. Compare and explain the forms that appear.

Example 1

As an example, the magnet units 170 in the straight sections (S1, S2) are arranged to have a size of 30 mm in depth and 40 mm in height, and the magnet units 170 in the curved sections (C1, C2) are arranged to have a size of 30 mm in depth and 34.5 mm in height. They were arranged in size, and the distance between the upper and lower magnet units 170 was 30.5 mm.

Comparative Example 1

As a comparative example, the magnet units 170 in the straight sections (S1, S2) are arranged to have a size of 30 mm in depth and 30 mm in height, and the magnet units 170 in the curved sections (C1, C2) are arranged to have a size of 30 mm in depth and 25 mm in height. and the distance between the upper and lower magnet units 170 was arranged to be 30 mm.

Figure 15 is a diagram showing the results of three-dimensional magnetic field computer simulation of Example 1 for magnet unit arrangement, and Figure 16 is an 875G isoline at the center of a pair of magnet units spaced apart in the slot direction of the example for magnet unit arrangement. This is a diagram showing the formation and the 875G isoline formation between slots.

Referring to FIG. 15, in the case of Example 1, as shown in the 875G isoline, which is the ECR resonance (Electron Cyclotron Resonance) area in (a), due to the magnetic field gradient in the portion where the magnet unit 170 is located and the slot 115 portion. Although the isoline appears uneven, it can be seen that the strength of the magnetic field formed inside the plasma chamber 140 is sufficient. From the isoline in (b), it can be seen that the magnetic field strength and gradient that allows hot electrons to rotate in the circumferential direction are effectively formed.

In addition, referring to FIG. 16, in the case of Example 1, it can be seen that the isoline formed between the pair of magnet units 170, as shown in (a), is formed by penetrating deep into the inside of the plasma chamber 140, It can be seen that the gradient of the magnetic field isoline within the plasma chamber 140 is formed in a “D” shape (plsitive curvature). According to the formation of this isoline, high-temperature electrons can exhibit excellent characteristics in securing plasma uniformity through induction and diffusion of B-field curvature drift.

In addition, as shown in (b), the isoline formed in the cross section between the slots 115 shows the result of reflecting the discontinuous arrangement of the magnet units 170 due to the structure of the slots 115. In contrast, by increasing the distance between a pair of magnet units 170 and arranging the magnet units continuously, the problem of the occurrence of a discontinuous section of the magnetic field isoline between the slots 115 and the slot 115 can be solved, but a pair of magnet units 170 Due to the long distance between the magnet units 170, the magnetic field isoline is formed adjacent to or in contact with the electromagnetic wave incident window 141, which is expected to cause problems with durability such as etching and heat loss of the electromagnetic wave incident window 141 by high-density plasma. do.

Figure 17 is a diagram showing the radial profiles of the magnetic field at the slot location and the upper and lower pair of magnet unit locations in Example 1 of the magnet unit arrangement.

Referring to FIG. 17, at the position between the magnet units 170 and the magnet units 170 facing each other as shown in (a), an ECR area is formed at a point 16.9 mm away from the electromagnetic wave incident window 141, (b) It was confirmed that an ECR area was formed at a point 9.8 mm away from the electromagnetic wave incident window 141 at a position between the slots 115 and the slots 115 facing each other as shown. At this time, the mirror ratio between the magnet units 170 is B _max /B _ecr of 1.86, and B _max /B _ecr between the slots 115 and 115 is 1.22, confirming that sufficient magnetic force is formed to trap electrons. You can.

Figure 18 is a diagram showing the results of three-dimensional magnetic field computer simulation of Comparative Example 1 for magnet unit arrangement, and Figure 19 is a diagram showing the 875G isoline at the center of a pair of magnet units spaced apart in the slot direction of Comparative Example 1 for magnet unit arrangement. This is a diagram showing the formation and the 875G isoline formation between slots.

Referring to FIG. 18, in the case of Comparative Example 1, the isoline is formed by the magnetic field gradient in the area where the magnet unit 170 is located and the slot 115, as shown in the 875G isoline, which is the ECR resonance (Electron Cyclotron Resonance) area. It can be seen that it shows a similar appearance to the example.

Referring to FIG. 19, in the case of Comparative Example 1, the isoline formed between the pair as shown in (a) does not show the appearance of being concentrated into the plasma chamber 140 compared to the embodiment, and as shown in (b) It can be seen that the isoline formed in the cross section between the slots 115 and the slot 115 shows a similar shape to that of the embodiment.

Figure 20 is a diagram showing the radial profiles of the magnetic field at the slot location and the upper and lower pair magnet unit locations of Comparative Example 1 with respect to the magnet unit arrangement.

Referring to FIG. 20, at the positions of the magnet unit 170 and the magnet unit 170 facing each other as shown in (a), an ECR area is formed at a point 10.4 mm away from the electromagnetic wave incident window 141, and (b) and It was confirmed that an ECR area was formed at a point 0.9 mm away from the electromagnetic wave incident window 141 at a position between the slots 115 and 115 that face each other. Therefore, in the case of the comparative example, it was confirmed that the ECR area was formed closer to the electromagnetic wave incident window 141 than in the example.

As shown in the comparative results of Example 1 and Comparative Example 1, the size and arrangement of the magnet units 170 can maintain a large distance between the ECR plasma formed in the plasma chamber 140 and the electromagnetic wave incident window 141, thereby preventing electromagnetic waves from being transmitted. Damage to the entrance window 141 by ECR plasma can be effectively prevented. Accordingly, there is an advantage in that damage to the electromagnetic wave incident window 141 can be prevented and durability of the plasma source unit 100 can be increased.

The plasma source unit 100 using a resonant waveguide according to an embodiment of the present invention surrounds the magnet units 170 to prevent interference with electromagnetic waves incident inside the plasma chamber 140 and has a flow path through which the coolant moves. A cooling structure forming a path may be provided. That is, the cooling structure can be configured to allow coolant to flow only around the magnet unit 170 without crossing the slot 115.

Figure 22 is a partially enlarged cross-sectional view for explaining the cooling structure at the slot position of the plasma source unit 100 by the resonance waveguide according to an embodiment of the present invention.

Referring to FIG. 22, for this purpose, the plasma source unit 100 using a resonant waveguide according to an embodiment of the present invention is disposed between the slots 115 and includes each straight section yoke surrounding the magnet unit 170. 180a) may include a pair of first cooling passages 201 passing vertically parallel to the slot 115 within the two side walls, and a pair of first cooling passages 201 of each straight section yoke 180a ( 201), a first vertical hole 202 and a first horizontal passage 203 in fluid communication, and first cooling passages adjacent to each other of straight section yokes 180a with a slot 115 in between. (201) may include a second vertical hole 204 and a second horizontal passage 205 for fluid communication, a first inlet 206 through which coolant is supplied, and a first outlet 207 through which coolant is discharged. there is.

As shown in FIG. 22, the pair of first cooling passages 201 penetrate the inside of the side surface of the straight section yoke 180a along a direction parallel to the slot 115, forming the straight section yoke 180a. It can be placed on the left and right sides of the pair of magnet units 170 that surround it.

In one embodiment, the first vertical hole 202 and the first horizontal passage 203 may be provided through the lower fixing plate 162. That is, the lower fixing plate 162 may be provided in a stacked structure of the first cover layer 161a located on the outside and the first flow path layer 161b located on the inside. For example, the first flow path layer 161b may be provided in the shape of a circular or oval plate, and the first cover layer 161a may be a square shape with a length less than or equal to the length of the straight sections S1 and S2. It is provided in the form of a plate and a U-shaped plate covering the curved sections (C1, C2), and the first cover layer (161a) in the shape of a square plate is the first flow layer (161b) in the straight sections (S1, S2). ) and the U-shaped plate-shaped first cover layer 161a may be laminated on the first flow path layer 161b in the curved sections C1 and C2. The first vertical hole 202 may be a through hole formed in the first flow path layer 161b, and the first horizontal flow path 203 may be a first cover layer 161a of the first flow path layer 161b. It may be a horizontal groove formed on the surface facing the. To elaborate, the first vertical hole 202 extends coaxially to each of the pair of first cooling passages 201 and is connected to the first cover layer 161a from a surface in close contact with the straight section yoke 180a. It may be a hole penetrating toward the facing surface, and the first horizontal flow path 203 is connected to the first vertical hole 202 on the surface facing the first cover layer 161a of the first flow path layer 161b. It may be a horizontal groove connected in fluid communication.

In one embodiment, the second vertical hole 204 and the second horizontal passage 205 may be provided through the upper fixing plate 161. That is, the upper fixing plate 161 may be provided in a stacked structure of a second cover layer 162a located on the outside and a second flow path layer 162b located on the inside. The second cover layer 162a may be provided in the same form as the first cover layer 161a. The second vertical hole 204 may be a through hole formed in the second flow path layer 162b, and the second horizontal flow path 205 may be a second cover layer 162a of the second flow path layer 162b. It may be a horizontal groove formed on the surface facing the. To elaborate, the second vertical hole 204 extends coaxially to each of the first cooling passages 201 adjacent to each other in the straight section yokes 180a adjacent to each other with the slot 115 in between, and the straight section It may be a hole penetrating from the surface in close contact with the yoke 180a to the surface facing the second cover layer 162a, and the second horizontal flow path 205 is the second cover of the second flow path layer 162b. There may be a transverse groove fluidly connected to the second vertical hole 204 on the surface facing layer 162a.

In one embodiment, the first inlet 206 may be provided on the upper fixing plate 161. That is, the first inlet 206 can supply coolant to one of the pair of first cooling passages 201 of the straight section yoke 180a through a through hole penetrating the upper fixing plate 161. To elaborate, the first inlet 206 is one of the pair of first cooling passages 201 of the straight section yoke 180a at one end of the straight section yokes 180a, that is, the other straight section yoke 180a. Cooling water can be supplied to the first cooling passage 201 that is not adjacent to the first cooling passage 201 of .

In one embodiment, the first outlet 207 may be provided on the upper fixing plate 161. That is, the first outlet 207 can discharge coolant from one of the pair of first cooling passages 201 of the straight section yoke 180a through a through hole penetrating the upper fixing plate 161. . To elaborate, the first outlet 207 is one of the pair of first cooling passages 201 of the straight section yoke 180a at the other end of the straight section yokes 180a, that is, the other straight section yoke 180a. Cooling water may be discharged from the first cooling passage 201 that is not adjacent to the first cooling passage 201 of .

Meanwhile, although not shown, according to another embodiment, the first vertical hole 202 and the first horizontal passage 203 may be disposed on the upper fixing plate 161, and the second vertical hole ( 204) and the second horizontal passage 205 may be disposed on the lower fixing plate 162. In this case, the first inlet 206 and the first outlet 207 may be disposed on the lower fixing plate 162. According to this other embodiment, the arrangement structure of the first and second vertical holes 204 and the first and second horizontal passages 205 is similar to the first and second horizontal passages 205 according to the above embodiment, except that their positions are different. Since the arrangement structure of the second vertical hole 204 and the first and second horizontal passages 205 is the same, a more detailed description will be omitted.

Meanwhile, the plasma source unit 100 using a resonant waveguide according to an embodiment of the present invention has a cooling structure for cooling the magnet units 170 in the curved sections C1 and C2 surrounded by the curved section yokes 180b. may further include.

FIG. 23 shows the curved section yoke shown in FIG. 1 expanded and is a diagram to explain the cooling structure for cooling the curved section permanent magnets.

Referring to FIG. 23, the cooling structure for cooling the magnet units 170 in the curved sections C1 and C2 has a magnetization direction in which each curved section yoke 180b is arranged along the curved sections C1 and C2. A plurality of second cooling passages 211 vertically penetrating the inside of the curved section yoke 180b parallel to the slot 115 between each of the pair of magnet units 170 parallel to the direction of the slot 115. It may include a third vertical hole 212 and a third horizontal passage 213 that allow fluid communication between the upper ends of the second cooling passages 211 adjacent to each other, and of the second cooling passages 211 adjacent to each other. It may include a fourth vertical hole 214 and a fourth horizontal passage 215 that allow fluid communication at the bottom, a second inlet 216 through which coolant is supplied, and a second outlet 217 through which coolant is discharged.

In one embodiment, the third vertical hole 212 and the third horizontal passage 213 may be provided through the lower fixing plate 162. That is, the third vertical hole 212 may be a through hole formed in the first flow path layer 161b, and the third horizontal flow path 213 may be a through hole formed in the first flow path layer 161b. It may be a horizontal groove formed on the surface facing (161a). Since the arrangement structure of the third vertical hole 212 and the third horizontal passage 213 is similar to that of the first vertical hole 202 and the first horizontal passage 203, a more detailed description will be omitted.

In one embodiment, the fourth vertical hole 214 and the fourth horizontal passage 215 may be provided through the upper fixing plate 161. That is, the fourth vertical hole 214 may be a through hole formed in the second flow path layer 162b, and the fourth horizontal flow path 215 may be a through hole formed in the second flow path layer 162b. It may be a horizontal groove formed on the surface facing (162a). Since the arrangement structure of the fourth vertical hole 214 and the fourth horizontal passage 215 is similar to the second vertical hole 204 and the second horizontal passage 205, a more detailed description will be omitted.

In one embodiment, the second inlet 216 may be provided on the upper fixing plate 161. That is, the second inlet 216 can supply coolant to the second cooling passage 211 located at one end of the curved section yoke 180b through a hole penetrating the upper fixing plate 161.

In one embodiment, the second outlet 217 may be provided on the upper fixing plate 161. That is, the second outlet 217 may discharge coolant from the second cooling passage 211 located at the other end of the curved section yoke 180b through a hole penetrating the upper fixing plate 161.

Meanwhile, although not shown, according to another embodiment, the third vertical hole 212 and the third horizontal passage 213 may be disposed on the upper fixing plate 161, and the fourth vertical hole ( 214) and the fourth horizontal passage 215 may be disposed on the lower fixing plate 162. In this case, the second inlet 216 and the second outlet 217 may be disposed on the lower fixing plate 162. The arrangement structure of the third and fourth vertical holes 214 and the third and fourth horizontal passages 215 according to this other embodiment is similar to that of the third and fourth horizontal passages 215 according to the above embodiment, except that their positions are different. Since the arrangement structure of the four vertical holes 214 and the third and fourth horizontal passages 215 is the same, a more detailed description will be omitted.

Hereinafter, a process in which the magnet units 170 of the plasma source unit 100 are cooled by the resonance waveguide according to an embodiment of the present invention will be described.

First, the cooling process of the magnet units 170 surrounded through the straight section yoke 180a is to cool the coolant toward the straight section yoke 180a disposed at one end of the straight section S1 and S2 through the first inlet 206. After flowing in, it passes through one of the first cooling passages 201 of the pair of first cooling passages 201, and then through the first vertical hole 202, the first horizontal passage 203, and the first vertical hole. While sequentially passing through 202, it flows into the remaining first cooling passage 201 of the pair of first cooling passages 201, and then flows into the remaining first cooling passage 201 and the second vertical hole. (204), the first cooling of the remaining one of the pair of first cooling passages 201 of the other straight section yoke 180a while sequentially passing through the second horizontal passage 205 and the second vertical hole 204. It flows into the first cooling passage 201 adjacent to the passage 201, repeats this sequential movement path of the coolant and zigzags through the straight section yokes 180a arranged in the straight sections S1 and S2, In the first cooling passage 201 in fluid communication with the first outlet 207 of the pair of first cooling passages 201 of the straight section yoke 180a disposed at the other end of the straight section S1 and S2, It can be discharged through the outlet 207.

In this way, the coolant does not cross the slot 115 in the straight sections S1 and S2, but passes through the inside of the straight section yokes 180a and moves to surround the magnet units 170, thereby forming the slots 115 and The magnet units 170 can be cooled through a cooling structure that does not cause interference to electromagnetic waves incident into the plasma chamber 140 through the electromagnetic wave incident window 141.

Meanwhile, the cooling process of the magnet units 170 surrounded through the curved section yoke 180b is performed by flowing coolant through the second inlet 216 into the second cooling passage 211 located at one end of the curved section yoke 180b. After flowing in, it sequentially passes through the third vertical hole 212, the fourth horizontal passage 215, the third vertical hole 212, and the second cooling passage 211, and this sequential movement path of the coolant Repeatedly passing through the curved section yoke (180b) disposed in the curved section (C1, C2) in a zigzag manner, the second outlet is in fluid communication with the second cooling passage (211) located at the other end of the curved section yoke (180b). It can be discharged through (217).

In this way, the plasma source unit 100 using a resonant waveguide according to an embodiment of the present invention uses cooling water to cool the magnet units 170 and the electromagnetic wave incident window 141 made of a dielectric, so the cooling efficiency is high and the plasma source unit 100 uses coolant. The durability of the plasma source unit 100 can be increased by preventing damage to the magnet units 170 and the electromagnetic wave incident window 141 due to heat, and the cooling structure is provided so that the coolant does not cross the slot 115. (115) and the electromagnetic wave incident window 141 does not cause interference to the electromagnetic waves incident on the plasma chamber 140, and thus the loss of electromagnetic waves incident into the plasma chamber 140 is prevented by water-cooled direct cooling. The structure can be implemented.

Figure 24 is a diagram for explaining the plasma source unit 100 using a resonance waveguide according to another embodiment of the present invention.

Meanwhile, in the plasma source unit 100 using a resonance waveguide according to another embodiment of the present invention, as shown in FIG. 24, the magnet unit 170 may be arranged left and right perpendicular to the direction of the slot 115. That is, the magnet unit 170 can be arranged left and right within the yokes 180a and 180b. At this time, the yokes 180a and 180b may be arranged so that the neighboring magnet units 170 with the slot 115 in between are disposed with opposing poles.

In this case, the magnetization direction formed by the pair of magnet units 170 is perpendicular to the direction of the slot 115, and the magnetic field formed by the pair of magnet units 170 may be formed to cross the slot 115. .

The size and arrangement of the magnet unit 170 of the plasma source unit 100 using a resonance waveguide according to another embodiment of the present invention may be the same as the plasma source unit using a resonance waveguide according to an embodiment of the present invention. Accordingly, the same action and effect of moving the ECR plasma away from the electromagnetic wave incident window 141 can be implemented.

Experimental Example 1 - SEM image and Raman spectrum data according to coating time

3D graphene nanostructures synthesized using a 3D graphene nanostructure coating device including a plasma source according to Example 1 under conditions of a hydrogen flow rate of 100 sccm and a methane flow rate of 50 sccm at different times of 7, 15, 30, and 60 minutes, respectively. A FE-SEM image of the graphene nanostructure measured at the same magnification is shown in Figure 5, and the Raman measurement results and relative intensities of major bands are shown in Figure 6.

Referring to Figure 6, the I _G / I _D ratio related to the defect density of the three-dimensional graphene nanostructure is about 2.1 to 2.8, which is due to the defects and nano-sized graphene-like domains of the three-dimensional graphene nanostructure using plasma. You can see that there is.

Experimental Example 2 - SEM image and Capacitance measurement results according to methane flow rate

Using the three-dimensional graphene nanostructure coating device including the plasma source according to Example 1, the hydrogen flow rate was fixed at 100 sccm, and the methane flow rate was 20, 50, and 100 sccm from the left. Three-dimensional graphene was synthesized for 30 minutes. The FE-SEM image of the graphene nanostructure measured at the same magnification (Х100,000 times) is shown in Figure 4, and the capacitance measurement results thereof are shown in Figure 7.

Referring to FIG. 4, when the numerical range of the preferred flow rate ratio according to the present invention is satisfied (center image of FIG. 4), it can be seen that the upper edge of the three-dimensional graphene nanostructure exhibits an orderly and uniform structure. However, in the present invention, If the lower and upper limits of the numerical range of the desirable flow ratio are below (left image of Figure 4) or exceeded (right image of Figure 4), the three-dimensional graphene nanostructure is not completely synthesized, or even if synthesized, the upper edge of the structure is irregular. You can see that it appears.

Also, referring to Figures 4 and 7, depending on the ratio of the synthesis gas hydrogen and methane of the three-dimensional graphene nanostructure, the synthesis of the structure may not be complete or the upper edge may be deformed. A structure that is not fully synthesized has low surface area utilization, and deformation of the top edge reduces the capacitance value due to low ion capture rate during charge storage.

Referring to Figures 5 and 7, it can be seen that as the synthesis time increases, the pore size between the structures increases and then converges. (The synthesis times in Figure 5 are 7, 15, 30, and 60 minutes from the left.) If the synthesis time is more than 15 minutes, the change in the size of the capacitance value is small, which means that the surface area of the tertiary graphene nanostructure has the maximum value. Able to know. It can be seen that the preferred synthesis time in this process is 15 minutes.

Experimental Example 3 - Plasma generation test

A plasma generation test was conducted for each pressure range in the 3D graphene synthesis process using the plasma source unit according to the present invention, and this is shown in FIG. 8.

Referring to Figure 8, the ECR plasma generation process pressure is 0.2 to 5 mTorr. It is possible to generate high-density plasma at low pressure and can be used in fine dry etching processes.

Claims (23)

A coating device capable of coating a three-dimensional graphene nanostructure on a metal thin film over a large area,
A vacuum process chamber including a roll-to-roll unit for transporting and recovering the metal thin film;
A plasma source unit coupled to one end of the vacuum process chamber; Includes,
A 3D graphene nanostructure coating device in which 3D graphene nanostructure synthesis and coating are performed in the vacuum process chamber.
According to paragraph 1,
A 3D graphene nanostructure coating device characterized in that transfer of the metal thin film, hydrogen plasma pretreatment, synthesis and coating of the 3D graphene nanostructure, and recovery of the metal thin film are performed simultaneously in one vacuum process chamber.
According to paragraph 1,
The plasma source unit,
An annular or elliptical central waveguide including a plurality of slots on the inner surface;
Electromagnetic wave transmission means for transmitting electromagnetic waves to the central waveguide;
an electromagnetic wave supply unit transmitting electromagnetic waves to the electromagnetic wave transmitting means; and
A three-dimensional graphene nanostructure comprising a plasma chamber positioned on an outlet side of the slot to seal the inside of the central waveguide and having an electromagnetic wave incident window through which electromagnetic waves introduced through the slot can be radiated to the outside. Coating device.
According to paragraph 1,
Reaction gas flows into the vacuum process chamber,
The reaction gas is a three-dimensional graphene nanostructure coating device, characterized in that hydrogen and methane gas have a flow rate ratio of 1:0.1 to 1.
According to paragraph 2,
A three-dimensional graphene nanostructure coating device, wherein the vacuum process chamber further includes a planar heater.
According to paragraph 1,
The roll-to-roll portion is a three-dimensional graphene nanostructure coating device characterized in that it includes a first roll portion and a second roll portion.
According to paragraph 3,
The electromagnetic wave transmitting means is a tuner installed on one side of the central waveguide and transmits electromagnetic waves from the electromagnetic wave supply unit into the central waveguide,
A transmission waveguide is installed between the central waveguide and the tuner, both ends of which are directly connected to the central waveguide and the tuner, so that electromagnetic waves from the electromagnetic wave supply unit are transmitted to the central waveguide through the transmission waveguide,
The waveguide of the electromagnetic wave supply unit is arranged to form a tangent to one side of the central waveguide,
The electromagnetic wave transmission means is a rod-shaped conductor that penetrates the center waveguide and the waveguide of the electromagnetic wave supply unit perpendicular to the tangent line,
The center waveguide includes a first straight right angle waveguide, a second straight right angle waveguide parallel to the first straight right angle waveguide, and a first curved right angle connecting the ends of the first and second straight right angle waveguides on one side to enable electromagnetic wave communication. A three-dimensional graphene nanostructure coating device comprising a waveguide and a second curved right-angle waveguide connecting the ends of the first and second straight right-angle waveguides on the other side to enable electromagnetic wave communication.
In clause 7,
The straight and curved right angle waveguides are in TE mode,
One of the two sides perpendicular to the electric field in the straight and curved right angle waveguides is facing inward,
A three-dimensional graphene nanostructure coating device, wherein the slot is formed on an inner surface of the straight right-angled waveguide.
In clause 7,
A three-dimensional graphene nanostructure coating device, characterized in that the straight right-angle waveguide is WR430, and the curved right-angle waveguide is WR284.
In clause 7,
The slot is an upright slot perpendicular to the electromagnetic wave circulation direction of the central waveguide, is located between the inner surface of the central waveguide and the electromagnetic wave incident window, and includes a magnet unit disposed between the slots, and the electromagnetic wave incident window is A three-dimensional graphene nanostructure coating device, characterized in that it is installed to seal the gap formed by the magnet units.
According to clause 10,
The magnet units are arranged in a pair up and down parallel to the slot direction to form a toroidal magnetic field in the central waveguide, and the magnetization direction formed by the pair of magnet units is parallel to the slot direction. A 3D graphene nanostructure coating device.
According to clause 10,
The magnet units are arranged in pairs on the left and right perpendicular to the slot direction,
A three-dimensional graphene nanostructure coating device, characterized in that the magnetization direction formed by the pair of magnet units is perpendicular to the slot direction, and the magnetic field formed by the pair of magnet units crosses the slot.
According to clause 12,
The path through which the electromagnetic waves transmitted from the slot between the two adjacent magnets with the slot in between are transmitted has a narrow entrance and a narrow entrance so that the electromagnetic waves from the slot expand while passing through the path and enter the inside of the center waveguide. A three-dimensional graphene nanostructure coating device characterized by a trapezoidal horizontal cross-section of the expanded outlet shape.
According to clause 13,
a yoke surrounding the pair of magnet units, disposed between the slots, and including a pair of cooling passages vertically penetrating parallel to the slots within two side walls;
a ring-shaped or oval-shaped upper fixing plate and a ring-shaped or oval-shaped lower fixing plate located inside the center waveguide and arranged to cover the upper and lower surfaces of the yoke along the traveling direction of the center waveguide;
an inlet through which coolant is supplied to one of the pair of cooling channels through a through hole penetrating the upper fixing plate; and
It includes an outlet through which coolant is discharged from one of the pair of cooling passages through a through hole penetrating the upper fixing plate,
Comprising one or more magnet units including a yoke between the inlet and outlet,
The lower fixing plate has a pair of non-penetrating vertical holes fluidly connected to the ends of a pair of cooling passages formed in the two side walls of the yoke, and fluidly connects the pair of vertical holes within the lower fixing plate. It includes a horizontal passage crossing the magnet unit,
The upper fixing plate has a pair of non-penetrating vertical holes fluidly connected to one of the pair of cooling conduits of the yoke and an end of the cooling conduit of the adjacent yoke, and the pair of vertical holes in the upper fixing plate. A three-dimensional graphene nanostructure coating device comprising a horizontal flow path crossing the slot connecting fluid communication in the.
According to clause 13,
a yoke surrounding the pair of magnet units, disposed between the slots, and including a pair of cooling passages vertically penetrating parallel to the slots within two side walls;
a ring-shaped or oval-shaped upper fixing plate and a ring-shaped or oval-shaped lower fixing plate located inside the center waveguide and arranged to cover the upper and lower surfaces of the yoke along the traveling direction of the center waveguide;
an inlet through which coolant is supplied to one of the pair of cooling passages through a through hole penetrating the lower fixing plate; and
It includes an outlet through which coolant is discharged from one of the pair of cooling passages through a through hole penetrating the lower fixing plate,
Comprising one or more magnet units including a yoke between the inlet and outlet,
The upper fixing plate has a pair of non-penetrating vertical holes fluidly connected to the ends of a pair of cooling passages formed in the two side walls of the yoke, and fluidly connects the pair of vertical holes within the upper fixing plate. It includes a horizontal passage crossing the magnet unit,
The lower fixing plate has a pair of non-penetrating vertical holes fluidly connected to one of the pair of cooling conduits of the yoke and an end of the cooling conduit of the adjacent yoke, and the pair of vertical holes in the lower fixing plate. A three-dimensional graphene nanostructure coating device comprising a horizontal flow path crossing the slot connecting fluid communication in the.
According to clause 14,
The upper or lower fixed plate has a laminated structure of a cover layer located on the outside and a flow path layer located on the inside, and the vertical hole of the upper or lower fixed plate is a through hole formed in the flow path layer, and the vertical hole of the upper or lower fixed plate is a through hole formed in the flow path layer. A three-dimensional graphene nanostructure coating device, wherein the horizontal channel is a horizontal groove formed on the surface of the channel layer facing the cover layer.
According to clause 14,
The upper or lower fixed plate has a laminated structure of a cover layer located on the outside and a flow path layer located on the inside, and the vertical hole of the upper or lower fixed plate is a through hole formed in the flow path layer, and the vertical hole of the upper or lower fixed plate is a through hole formed in the flow path layer. A three-dimensional graphene nanostructure coating device, wherein the horizontal channel is a horizontal groove formed on the surface of the channel layer facing the cover layer.
A first step in which hydrogen plasma pretreatment is performed on the metal thin film supplied through the first roll unit inside the vacuum process chamber;
A second step of synthesizing and coating a three-dimensional graphene nanostructure on the metal thin film; and
A third step of recovering the metal thin film synthesized and coated with the three-dimensional graphene nanostructure through a second roll unit in a vacuum process chamber; Coating method of a three-dimensional graphene nanostructure comprising a.
According to clause 18,
A reaction gas containing hydrogen and methane gas is introduced into the vacuum process chamber,
A three-dimensional graphene nanostructure coating device, characterized in that the hydrogen and methane gases are introduced at a flow ratio of 1:0.1 to 1.
According to clause 18,
A three-dimensional graphene nanostructure coating device, characterized in that the vacuum process chamber maintains a process pressure of 1 to 3 mTorr.
According to clause 18,
The second step is a method of coating a three-dimensional graphene nanostructure, characterized in that it is a step of synthesis for 1 to 60 minutes.
metal thin film; and
A three-dimensional graphene nanostructure manufactured according to the coating method for a three-dimensional graphene nanostructure according to claims 18 to 22, and having a specific capacitance of 2.0 F/cm ² or more.
According to clause 22,
A three-dimensional graphene nanostructure with a pore size of 10 to 300 nm.