KR101369779B1 - Vertically aligned 3-dimensional graphene structure and a fabrication thereof - Google Patents

Abstract

The present invention relates to a vertically arranged graphene three-dimensional structure and a method for manufacturing the same, and more particularly, a support layer is formed on a substrate by an electrospray method, and graphene is formed thereon, wherein the graphene is formed on the substrate. It relates to a three-dimensional structure and its manufacturing method arranged in the vertical direction with respect to.
As the three-dimensional structure according to the present invention has a structure in which the graphene is stacked so that the crystal plane is perpendicular to the substrate, it is possible to obtain a new effect that can not be realized in the conventional two-dimensional structure, or to expand the application field.

Description

Vertically aligned 3-dimensional graphene structure and a fabrication method thereof

The present invention relates to a vertically arranged graphene three-dimensional structure having a laminated structure arranged so that the crystal plane is perpendicular to the substrate and a method of manufacturing the same.

Graphene is one of several carbon structures such as diamond, carbon nanotubes, and fullerenes. It is a two-dimensional structure consisting of a honeycomb structure in which carbon is connected like a net.

Such graphene is not only high in strength and thermal conductivity, but also has excellent electrical conductivity, and has good characteristics in maintaining electrical conductivity even when stretched or folded.

As one of the typical applications, graphene has potential as an element of ultra-high speed transistor through structural modification of nano ribbon graphene, bilayer graphene, nanomesh graphene, etc. due to the field effect characteristics. A study was also published [YM Lin and Phaedon Avouris, “Strong Suppression of Electrical Noise in Bilayer Graphene Nanodevice,” Nano Lett ., Feb. 2008, pp. 2119-2125; Jingwei Bai, Xing Zhong, Shan Jiang, Yu Huang, and Xiangfeng Duan, “Graphene Nanomesh,” Nature Nanotech ., Feb. 2010, pp. 190-194; BJ Kim, H. Jang, SK Lee, BH Hong, JH Ahn, and JH Cho, “High-Performance Flexible Graphene Field Effect Transistors with Ion Gel Gate Dielectrics ?,” Nano Lett ., 2010, pp. 3464-3466]

In addition, it is applied to biomimetic devices by using electrical, mechanical, and thermal properties, and shows excellent characteristics of large displacement and fast response speed even at low power, and displacement increases with increasing temperature [Shou-En Zhu et al . , “Graphene-based Bimorph Microactuators,” Nano Lett ., Jan. 2011, pp. 997-981]

And, Korean Patent Publication No. 2011-0105408 discloses a step of forming a lower electrode layer on a substrate, b) forming a graphene oxide layer on the formed lower electrode layer, and c) an upper electrode on the formed graphene oxide layer Through the step of forming a layer, it is proposed to manufacture a flexible resistance change memory device using a graphene oxide.

In addition, Thomas Mueller et al. Predicted that the characteristics of graphene could be used as ultrafast photo detectors because they operate in a wider wavelength band and have very fast response speeds. [Thomas Mueller, Fengnian Xia, and Phaedon Avouris, “Graphene Photodetectors for High- Speed Optical Communications, ”Nature Photonics, Mar. 2010, pp. 297-301.

In addition, the results of the transfer of graphene grown by CVD to the surface of metamaterials were measured [Nikitas Papasimakis, Zhiqiang Luo, Ze Xiang Shen, Francesco De Angelis, Enzo Di Fabrizio, Andrey E. Nikolaenko, and Nikolay]. I. Zheludev, “Graphene in a Photonic Metamaterial,” Optics Express , Apr. 2010, pp.8353-8359]

As such, depending on the various characteristics of graphene, the field of application is very diverse and its application potential is also very broad.

Meanwhile, graphene was first introduced to researchers through mechanical exfoliation (also known as scotch tape) in 2004, and then used chemical synthesis, chemical vapor deposition (CVD), and epitaxy synthesis. Is manufactured. Thus prepared graphene is laminated in a two-dimensional structure, and does not have a vertical electrical conductivity.

Specifically, Japanese Patent Laid-Open Publication No. 22-153793 proposes a technique for laminating graphene horizontally through a CVD method, and Korean Patent Publication No. 2011-0081519 discloses graphene nanostructures using a self-assembled material. Doing.

The graphenes proposed in these patents have a vertically stacked structure, but the arrangement of graphene shows that the crystal plane is horizontally deposited so that the graphene itself remains a two-dimensional structure.

The electrical conduction of graphene tends to move electrons along the edges of graphene, so if graphene is formed in a three-dimensional structure rather than a two-dimensional structure, unexpected effects can be obtained in two dimensions. have.

Republic of Korea Patent Publication No. 2011-0105408 Japanese Patent Laid-Open No. 22-153793 Republic of Korea Patent Publication No. 2011-0081519

Y-M Lin and Phaedon Avouris, “Strong Suppression of Electrical Noise in Bilayer Graphene Nanodevice,” Nano Lett., Feb. 2008, pp. 2119-2125 Jingwei Bai, Xing Zhong, Shan Jiang, Yu Huang, and Xiangfeng Duan, “Graphene Nanomesh,” Nature Nanotech., Feb. 2010, pp. 190-194 B.J. Kim, H. Jang, S.K. Lee, B.H. Hong, J.H. Ahn, and J.H. Cho, “High-Performance Flexible Graphene Field Effect Transistors with Ion Gel Gate Dielectrics,” Nano Lett., 2010, pp. 3464-3466 Shou-En Zhu et al., “Graphene-based Bimorph Microactuators,” Nano Lett., Jan. 2011, pp. 997-981 Thomas Mueller, Fengnian Xia, and Phaedon Avouris, “Graphene Photodetectors for High- Speed Optical Communications,” Nature Photonics, Mar. 2010, pp. 297-301 Nikitas Papasimakis, Zhiqiang Luo, Ze Xiang Shen, Francesco De Angelis, Enzo Di Fabrizio, Andrey E. Nikolaenko, and Nikolay I. Zheludev, “Graphene in a Photonic Metamaterial,” Optics Express, Apr. 2010, pp. 8383-8359.

Therefore, the present inventors believe that if the graphene is manufactured as a three-dimensional structure, while obtaining a new effect that can not be realized in the conventional two-dimensional structure or expanding the application field, while continuing to study the graphene, Focusing on the fact that there is a tendency for electricity to flow along the edges, graphene was deposited by electrospray, and as a result, the present invention was completed by finding that the graphene is disposed vertically instead of being deposited flat.

Accordingly, an object of the present invention is to provide a vertically arranged graphene three-dimensional structure having a three-dimensional structure, which has not been proposed anywhere in the prior art.

In addition, another object of the present invention is to easily form the vertically arranged graphene three-dimensional structure in a large area, and to provide a manufacturing method with a simple process.

In order to achieve the above object, the present invention is a substrate; A support layer formed on the substrate; And it provides a vertically arranged graphene three-dimensional structure comprising a graphene supported by the support layer and arranged in a vertical direction.

In addition, the present invention is to prepare a substrate, a support layer solution and a graphene solution, respectively, and three-dimensional structure through the process of sequentially electrospraying the support layer solution and graphene solution on the substrate using an electrospray apparatus equipped with a nozzle It provides a method of manufacturing.

As the three-dimensional structure according to the present invention has a stacked structure so that the crystal plane of the graphene in the vertical direction with respect to the substrate, it is possible to obtain a new effect that can not be realized in the conventional two-dimensional structure, or to expand the application field.

1 is a three-dimensional cross-sectional view showing a graphene three-dimensional structure proposed in the present invention.
2 is a cross-sectional view of Fig.
Figure 3 is a schematic diagram showing a manufacturing method of the graphene three-dimensional structure according to the present invention.
Figure 4 shows the directivity of the graphene in the electrospray process, (a) is vertical, (b) shows the movement in the horizontal direction.
5 is a schematic view showing the electrospray apparatus used in the present invention.
6 (a) and (b) is a scanning electron micrograph showing the graphene prepared in Example 1.
7 is a scanning electron micrograph of the vertically arranged graphene three-dimensional structure prepared in Example 1, (a) shows the front, (b) to (d) shows a cross section.
FIG. 8 (a) shows graphene prepared by CVD, and FIG. 8 (b) shows graphene prepared by air spray.

Hereinafter, the present invention will be described in more detail.

In the present invention, the graphene is arranged in a vertical direction with respect to the substrate to propose a structure that can be applied in three dimensions that the electrical properties of the conventional graphene was expressed only in two dimensions.

1 is a three-dimensional cross-sectional view showing a graphene three-dimensional structure proposed in the present invention, Figure 2 is a cross-sectional view thereof. In this case, although the graphene is shown to have a high degree of alignment in order to facilitate understanding in FIGS. 1 and 2, the graphene is substantially irregularly stacked at a predetermined angle so that its crystal plane is not parallel to the substrate. In addition, for convenience, each graphene is illustrated to be spaced at a predetermined interval to express the alignment in the vertical direction, but the graphene is substantially stacked at an empty interval to form one layer.

Referring to FIG. 1, in the graphene three-dimensional structure 10, the support layer 13 is positioned on the substrate 11, and the graphene 15 is vertically arranged on the support layer 13. As shown in FIG. 2, a portion of the graphene 15 is present in a state perpendicular to the support layer 13.

Such a structure is stacked so that the crystal plane of the graphene is perpendicular to the substrate, and there is a great difference in morphology as well as a structural difference from a structure in which graphene manufactured by a method such as CVD is stacked horizontally.

That is, the graphene three-dimensional structure 10 may secure electrical characteristics in the vertical direction (Z-axis direction) that could not be expected in the horizontally stacked graphene having a two-dimensional structure. In addition, in the image as shown in FIG. 8 (a), in the laminated structure such as CVD, the surface was smoothly stacked sequentially in order, whereas the graphene three-dimensional structure 10 according to the present invention is shown in FIG. As shown in d), the surface roughness of the graphene 15 thin film is greatly improved due to the vertical alignment of the graphene.

In the graphene three-dimensional structure 10 described above, the substrate 11 is not particularly limited in the present invention, and may be any material commonly used as a substrate (silicon substrate, glass substrate, or polymer substrate). For example, glass substrates such as single silicon, p-Si, alkali silicate glass, alkali-free glass, quartz glass, silicon substrates, acrylates, polycarbonates, resin substrates such as polyethylene naphthalate (PEN), polyethylene terephthalate ( Polymers such as PET) and polyamide may be used. The thickness is also used within a conventional range, and for example, 0.1 to 10 mm and 0.3 to 5 mm are preferable.

The substrate 11 may be used as it is depending on the application of the graphene three-dimensional structure 10, and may be applied to various devices by removing only the substrate 11 if necessary.

As shown in FIGS. 1 and 2, the support layer 13 is used for fixing and supporting the graphene 15 arranged in the vertical direction so as to maintain the arrangement state and to be attached to the substrate 11 well. use.

The support layer 13 may be formed using both electrically insulating or conductive materials, and the selection of the material may vary depending on the application of the graphene three-dimensional structure 15. For example, when used for the purpose of the electrode, the support layer 13 may be made of a conductive polymer.

As a material that can be used as the support layer 13, any material that can fix or support the graphene 15 as well as a polymer known as a binder or a binder may be used. In one example, the support layer 13 together with a polymer having insulating properties such as polyacrylate, polymethacrylate, polystyrene, polyester, polyamide, polyimide, polyolefin, cellulose, ethyl cellulose, polyvinyl butyral, polyacrylic ester, etc. , Polymers having conductivity such as polyaniline, polypyrrole, polyacetylene, polythiophene, PEDOT (poly (3,4-ethylenedioxythiophene), etc. may be used. In one embodiment of the present invention, a PEDOT may be used for a substrate. The graphene was arranged vertically.

The thickness of the support layer 13 is also not limited in the present invention, and may be appropriately adjusted within a thickness range of 0.5 μm to 0.1 mm. The thickness of the support layer 13 may vary sufficiently depending on the purpose (ie, fixing and support) of the support layer 13 and the specific purpose (that is, conductivity, etc.) according to the use, which can be appropriately selected by those skilled in the art. .

In addition, the support layer 13 may be laminated in a single layer or multiple layers, wherein each layer is made of the material mentioned above.

The graphene three-dimensional structure according to the present invention having the above-described structure is manufactured through an electrospray process that can be deposited in the form of droplets by an electric field rather than a conventional CVD or simple solvent spray process.

As mentioned above, in the case of graphene 15, since the electrons are transported along the edges, the graphene 15 is deposited on the substrate 11 by the flow of an electric field applied during the electrospray process. You can adjust the direction of graphene.

Figure 3 is a schematic diagram showing a manufacturing method of the graphene three-dimensional structure according to the present invention, Figure 4 shows the directivity of the graphene during the electrospray process, (a) is a vertical, (b) is a stack in the horizontal direction Shows.

Referring to FIG. 3, the nozzle tip to which the graphene solution is sprayed and the substrate 11 are perpendicular to each other, and an electric field is applied thereto to adjust the flow of the electric field to be perpendicular to the graphene sprayed from the nozzle tip. 15 is transferred to the substrate 11 in a direction perpendicular to the crystal plane of the graphene 15 as shown in FIG. 4 (a) as the electric field flows. At this time, as shown in Figure 4 (b) due to the nature of the graphene, since the flow or transfer in the horizontal direction does not occur, it enables the alignment of the graphene 15 in the vertical direction. However, in a general spraying process in which an electric field is not formed, a flow as shown in FIG. 4B is possible, and thus lamination in the horizontal direction of the graphene 15 as shown in FIG. 7B may be performed.

In this case, in order to effectively arrange the graphene 15 in the vertical direction, the substrate 11 is disposed on the lower side and the nozzle is disposed on the upper side, so that the graphene 15 is effectively transferred to the substrate 11 by gravity with an electric field. It is desirable to exclude elements that would interfere with the stacking of the graphene 15 by other factors than the electric field. As an example, as shown in FIG. 5, the nozzles are disposed horizontally with respect to the direction of gravity and the substrate 11 is disposed perpendicularly to the direction of gravity to exclude the influence of gravity.

In addition, in the present invention, the formation of the support layer 13 together with the lamination of the graphene 15 may also be performed by electrospray, thereby effectively fixing the graphene 15 to the substrate 11 and increasing process convenience.

The electrospray apparatus for producing the graphene three-dimensional structure is not particularly limited in the present invention, it is possible to use a device equipped with two nozzles as shown in FIG. In this case, the electrospray device may be variously modified by those skilled in the art, and is illustrated to be exaggerated for understanding, and a known device or configuration required for electrospray may be added to each element. For convenience, two syringes, pumps, and potentiometric generators are shown for spraying the support layer solution and the graphene solution for convenience, but they may be provided in one to plural numbers by using a solution or an electrical connection method. That is, the syringe and pump of each solution can be provided according to the number of solutions used, and they can be used in electrical connection with one potential difference generator.

In particular, in the apparatus of FIG. 5, the nozzles and the substrates are arranged to be horizontal and vertical with respect to the direction of gravity, respectively, in order to exclude the influence of gravity.

Referring to FIG. 5, the electrospray apparatus 100 stores the support layer solution and the graphene solution for electrospray, respectively, and the syringes 101a and 101b equipped with the nozzles and the support layer solution in the syringes 101a and 101b. The syringe pumps 103a and 103b for supplying the graphene solution, the potential difference generating devices 105a and 105b for forming an electric field between the substrate 11 and the syringes 101a and 101b, and the support layer solution and the graphene solution And a stage 107 for supporting the substrate 11 to be deposited.

It describes a method for producing a graphene three-dimensional structure in more detail using the apparatus 100 described above.

First, the substrate 11 to be laminated on the electrospray apparatus 100 is positioned.

Next, the support layer solution and the graphene solution are prepared, and the solution is injected into the syringes 101a and 101b using the syringe pumps 103a and 103b, respectively. At this time, the nozzles of the syringes 101a and 101b are disposed to be perpendicular to the substrate 11.

Next, electricity is applied to the nozzle and the stage 107 by using the potential difference generating device 105a to form an electric field having a flow in the vertical direction inside the chamber.

Next, the droplet of support layer solution is sprayed on the board | substrate 11 from the syringe 101a, and the support layer 13 is formed.

Next, after the support layer 13 is formed, the graphene solution is sprayed from the syringe 101b into the droplet state using the potential difference generator 105b connected to the syringe 101b containing the graphene solution on the support layer 13. Lay graphene on.

Next, after completion of spraying the graphene solution, the support layer 13 and the graphene are formed on the substrate 11 by removing the support layer solution and the solvent or various additives contained in the graphene solution through a drying process, and the graphene Obtain a vertically arranged three-dimensional structure.

At this time, the drying conditions vary depending on the solvent used, it is carried out in a temperature range of 15 ~ 200 ℃ to remove the solvent sufficiently.

The vertically arranged graphene three-dimensional structure manufactured by the above steps has an electric field during the electrospray process, together with factors such as the size of the graphene, the support layer material, the solvent used, the type and content of various additives, and the concentration. The morphology can be controlled by adjusting factors such as the intensity, the distance between the nozzle and the substrate, the temperature, and the flow rate.

The graphene to be used is not limited to the manufacturing method, and can be used directly by purchasing the graphene in the form of a flake (flake) directly or commercially available. For example, in the present embodiment was prepared directly through the chemical exfoliation method was used having a width of 2-3 micrometers.

The solvent usable in the support layer solution and the graphene solution may be sufficiently dissolved or dispersed therein, and in the case of the support layer solution, various solvents may be selected depending on the material of the support layer. Typically, water methanol, ethanol, propanol, isopropanol, butanol, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethylethyl ether, methyl methoxy propionate, ethyl ethoxy propionate (EEP ), Ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol methyl acetate, diethylene glycol ethyl acetate, acetone , Methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pyrrolidone (NMP), γ-butyrolactone , Diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), methyl cellosolve, ethyl cellosol , Diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, and the like, which can be used individually or in combination, and in the present invention, dimethyl Formamide was used.

The content of the solvent may be used in a volume ratio of 0.1 to 1000 ml with respect to the support layer material or 1 g of graphene, and the content of the solvent may have a concentration such that the nozzle is not clogged during electrospray. In other words, when the concentration is too high, the electrospray is not easy, on the contrary, when the concentration is too low, the electrospray time is increased to increase the overall process time. In addition, since the thickness of each layer may also vary according to the concentration of each solution, the process is performed by setting the optimum concentration in consideration of the flow rate and time described below.

Where necessary, the support layer and the graphene solution additionally include a dispersant to increase dispersion stability, and additives such as surfactants and plasticizers, thickeners, diluents, etc. to form droplets upon electrospray. That is, the support layer and the graphene solution used for the electrospray should have high dispersion stability so that it can be maintained for a long time without agglomeration, agglomeration or sedimentation, and should be able to form stable droplets without clogging the nozzle during electrospray. This property is to select each composition constituting the solution and to limit the content range, if necessary, in the case of graphene solution by applying ultrasonic waves to maintain a uniform dispersion state without precipitation in the solution.

In addition to the above factors, in consideration of the factors in the electrospray process, the distance between the nozzle and the substrate and the strength of the magnetic field in this case are also considered important so that the graphene ejected from the nozzle can be transported in a direction perpendicular to the support layer. Should be.

Specifically, if the distance between the nozzle and the substrate is not sufficient, the graphene may not have sufficient vertical orientation, and if it is too far, the time may increase the manufacturing time, so the distance between the nozzle and the substrate may be 1 to 15 cm. Adjust to make it work.

In addition, electricity is applied for spraying in the state of droplets, in which the smaller the voltage of the applied electricity tends to form smaller droplets. Thus, a voltage is applied in the range of 5-50 kV, preferably 10-25 kV, so that one graphene can be present in one droplet, i.e., to form a micron level droplet, for a uniform arrangement of graphene.

In addition, a high voltage may be applied when the substrate and the nozzle are far away, and a low voltage may be applied when the substrate and the nozzle are close, and the size of the voltage may be appropriately considered along with the distance between the nozzle and the substrate. The voltage applied between and the substrate was performed at 20 kV.

In addition, the flow rate as one parameter in the electrospray may be considered the flow rate of the support layer solution and the graphene solution to control the thickness of the support layer and the graphene layer. That is, as the flow rate of each solution is higher, the thickness of each layer may increase as the content of the supporting layer material and the graphene is increased. Preferably it is carried out in the range of 0.001 to 10 ml / min, in the embodiment of the present invention by depositing for 5 minutes at 0.01 ml / min to obtain a graphene thin film of about 6 ㎛ thickness.

The parameters related to the thickness of the support layer and the graphene layer, together with the flow rate, may include a process time. Since the thickness increases as the process time increases, an appropriate process time is set according to the use of the three-dimensional structure.

The vertically arranged graphene three-dimensional structure manufactured through the above steps has a surface and internal characteristics as shown in FIG. 7, so that it is possible to obtain new effects or to expand an application field not realized in the conventional two-dimensional structure. have.

Furthermore, the method according to the present invention is not only advantageous in terms of cost compared to the expensive equipment for conventional deposition, but also can shorten the manufacturing time and can be easily processed in a mass production process as it can be processed at room temperature and atmospheric pressure. Applicable

[Example]

Hereinafter, preferred embodiments and experimental examples of the present invention will be described. However, the following examples are only preferred examples of the present invention, and the present invention is not limited by these examples.

Example 1: Preparation of a vertically arranged graphene three-dimensional structure

(1) graphene manufacturing

Graphite oxide (GO) was prepared using modified Hummers method and Offeman method [1. WS Hummers, RE Offeman, J. Am. Chem. Soc . 1958, 80, 1339].

For exfoliation of graphite, 10 mL of sulfuric acid was mixed in 50 mL of distilled water in a 35 W 5 ° C water bath for 3 hours. Then 1 g of graphite, 10 mL of potassium hydroxide and dilute sulfuric acid were stirred for 3 hours in an ice bath using a Teflon-treated magnet to prepare a thick paste. While the color of the graphite mixed solution changed from black to dark brown, 100 mL of distilled water was added, followed by the slow addition of 10 mL of hydrogen peroxide with oxidant to prepare GO, wherein the color of the solution changed from dark brown to yellow.

GO precipitates were separated and collected for 30 minutes from a GO suspension in a high speed centrifuge at 15000 rpm. The obtained GO was washed with 200 mL of 5% hydrochloric acid and washed repeatedly with distilled water until the pH of the solution reached 7.

The GO sheet suspension of the obtained aqueous solution was reduced to graphene colloid using hydrazine monohydrate as reducing agent in DMF. The mixture of RGO (reduced graphene oxide) and DMF was heated in a water bath to 90 W 5 ° C for 24 h. As a result, black solids were deposited in the mixture.

The RGO-hydrazine obtained above was then diluted six times with DMF to produce a homogeneous colloidal suspension of reduced graphene oxide (RGO) in DMF solvent. Next, ultrasonic waves were applied for 10 minutes to obtain a stable and homogeneous RGO dispersion. As a result, the RGO was stable for several weeks at room temperature. During this period samples were prepared and characterized.

The prepared graphene is shown in FIG. Referring to Figure 5 (a) and (b), it can be seen that the graphene prepared through the above step has a width of 2 to 3 microns.

(2) Preparation of graphene solution and support layer solution using electrospray

0.001 g of graphene prepared in (1) was dispersed in 1 ml of DMF to prepare a graphene solution. In addition, a support layer solution was prepared by dissolving 1 g of PEDOT and 5 ml of DMF.

These graphene solutions and support layer solutions were injected into syringes of the electrospray apparatus, respectively. A silicon wafer was used as the substrate, and the distance between the needle of the syringe and the substrate was adjusted to 10 cm. The deposition was performed by applying an electric field of 20 kV between the needle and the substrate.

First, deposition was performed on the substrate with a support layer solution for 5 minutes, and then deposited on the support layer through a nozzle of graphene solution to a thickness of about 6 μm.

Then dried at 100 ℃ to obtain a vertically arranged graphene three-dimensional structure.

Experimental Example 1: Analysis of the vertically arranged graphene three-dimensional structure

In order to confirm the characteristics of the obtained graphene / PEDOT film, it was measured using an electric field scanning electron microscope (FE-SEM, Quanta 200 FEG, FEI).

7 is a scanning electron micrograph of the vertically arranged graphene three-dimensional structure prepared in Example 1, (a) shows the front, (b) to (d) shows a cross section. At this time, the position of the three-dimensional structure of (b) to (d) is a structure stacked in order from the substrate / PEDOT / graphene from above.

Referring to FIG. 7A, a sharp white area was observed as a result of observing the three-dimensional structure from the front, and this white area means an edge when the graphene is viewed vertically. Referring to Figure 7 (b) to (d), it can be seen that the graphene is vertically arranged at an angle on the PEDOT film.

This can be clearly compared to graphene prepared by conventional CVD or air spray method.

Figure 8 (a) shows the graphene prepared by CVD, Figure 8 (b) shows the graphene prepared by the air spray method. In the case of CVD, graphene has a very smooth surface, and in the case of the air spray method, it is also found to be flat.

Claims (17)

Board;
A support layer formed on the substrate; And
Graphene supported by the support layer and arranged in a vertical direction,
In this case, the support layer is a vertical arrangement, characterized in that it comprises a conductive polymer selected from the group consisting of polyaniline, polypyrrole, polyacetylene, polythiophene, poly (3,4-ethylenedioxythiophene) and combinations thereof Pin three-dimensional structure. The vertically arranged graphene three-dimensional structure of claim 1, wherein the substrate is a silicon substrate, a glass substrate, or a polymer substrate. The method of claim 1, wherein the substrate is a single silicon, p-Si, alkali silicate-based glass, alkali-free glass, quartz glass, silicon substrate, acrylate, polycarbonate, polyethylene naphthalate (PEN), polyethylene terephthalate (PET) And vertically arranged graphene three-dimensional structure comprising one selected from polyamides and combinations thereof. delete delete The support layer solution and the graphene solution are respectively stored for the electrospray, syringe with a nozzle,
A syringe pump for supplying a support layer solution and a graphene solution to the syringe,
A potential difference generator for forming an electric field between the substrate and the syringe, and
Using an electrospray device having a stage for supporting a substrate on which a support layer solution and a graphene solution are deposited,
Prepare a substrate, a support layer solution and a graphene solution respectively,
By using an electrospray device equipped with a nozzle is prepared through a process of sequentially spraying the support layer solution and the graphene solution on the substrate and then drying,
In this case, the support layer solution may include a first conductive polymer selected from the group consisting of polyaniline, polypyrrole, polyacetylene, polythiophene, poly (3,4-ethylenedioxythiophene), and combinations thereof. Method of manufacturing a graphene three-dimensional structure of the vertical arrangement of the term. The method of claim 6, wherein the support layer solution comprises a conductive polymer and a solvent. The method of claim 6, wherein the graphene solution comprises graphene and a solvent. The method of claim 7 or 8, wherein the solvent is water, methanol, ethanol, propanol, isopropanol, butanol, ethyl acetate, butyl acetate, diethylene glycol dimethyl ether, diethylene glycol dimethyl ethyl ether, methyl methoxy pro Cypionate, ethyl ethoxypropionate (EEP), ethyl lactate, propylene glycol methyl ether acetate (PGMEA), propylene glycol methyl ether, propylene glycol propyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene Glycol methyl acetate, diethylene glycol ethyl acetate, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, dimethylformamide (DMF), N, N-dimethylacetamide (DMAc), N-methyl-2-pi Ralidone (NMP), γ-butyrolactone, diethyl ether, ethylene glycol dimethyl ether, diglyme, tetrahydrofuran (THF), Methyl cellosolve, ethyl cellosolve, diethyl ether, diethylene glycol methyl ether, diethylene glycol ethyl ether, dipropylene glycol methyl ether, toluene, xylene, hexane, heptane, octane, and mixed solvents thereof Method for producing a vertically arranged graphene three-dimensional structure comprising one selected from the group. The method of claim 6, wherein the support layer solution of the vertically arranged graphene three-dimensional structure characterized in that it further comprises one type of additive selected from the group consisting of a dispersant, surfactant, plasticizer, thickener, diluent and combinations thereof. Way. The graphene solution of claim 6, wherein the graphene solution further comprises one additive selected from the group consisting of dispersants, surfactants, plasticizers, thickeners, diluents, and combinations thereof. Manufacturing method. The method of claim 6, wherein the distance between the substrate and the nozzle is 1 to 15 cm. The method of manufacturing a vertically arranged graphene three-dimensional structure according to claim 6, wherein the electric field is applied with a voltage of 5 to 50 kV. delete 7. The method of claim 6, wherein the electrospray device is arranged such that the syringe nozzle is perpendicular to the substrate. 7. The method of claim 6, wherein the electrospray device is arranged such that the syringe nozzles are horizontal with respect to the direction of gravity. An electrode comprising the vertically arranged graphene three-dimensional structure of claim 1.

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