KR20190129808A - Process for forming hybrid nanostructure on graphene - Google Patents

Abstract

The present invention relates to a forming method of a hybrid nano-structure and, more specifically, to a hybrid nano-structure controlling morphology which is obtained by controlling the thickness of a gold metal layer into a certain range and to a nano-electric device comprising the same, which exhibits stable electrical properties and has a DC mode.

Description

Process for forming hybrid nanostructure on graphene

A method of forming a hybrid nanostructure on graphene is provided. More particularly, the present invention relates to a method of forming a hybrid nanostructure on graphene by controlling the morphology of the nanostructure by controlling the thickness of the gold metal layer.

Graphene, a monolayer formed from a two-dimensional honeycomb crystal structure of carbon atoms, has recently exhibited significant electronic, optical, chemical and mechanical properties, including quantum electronic transport, optical transparency, chemical stability and mechanical durability. Because of this, attention has been drawn to nanoscale functional devices.

Graphene is one of the most promising next-generation transparent conductive materials to replace conventional transparent conductive oxides (TCO) such as indium tin oxide (ITO) and fluorotin oxide (FTO) in optoelectronic devices, including solar cells and light emitting diodes. Is one of.

Meanwhile, composite nanostructures obtained by growing nanomaterials on various substrates including indium tin oxide (ITO), GaN, and AlN have been widely used in piezoelectric devices. In this composite nanostructure, a graphene layer is interposed between the substrate and the nanostructure, thereby incorporating the excellent thermal, mechanical properties, and excellent conductivity of graphene, thereby making it possible to manufacture a superior nanoelectric device.

However, since it is difficult to control the orientation of the nanostructures formed on the graphene layer, it is difficult to obtain nanostructures of stable quality because nanowires are mainly grown in an inclined direction rather than in a direction perpendicular to the graphene layer. It was.

In addition, nanostructures having various shapes such as nanowires, nanorods, and nanotubes may be formed according to conditions when nanomaterials are grown, and electrical properties of piezoelectric elements including the nanostructures may also be formed according to various shapes of such nanostructures. There may be a need to control the morphology of the nanostructures as they may vary.

The first problem to be solved by the present invention is to provide a method for forming a hybrid nanostructure on graphene.

The second problem to be solved by the present invention is to provide a composite nanostructure comprising a hybrid nanostructure formed by the above method.

It is a third object of the present invention to provide a nano electric device including the composite nanostructure.

According to an aspect of the present invention to achieve the first object,

Forming a graphene layer on the substrate;

Forming a gold metal layer on the graphene layer;

Chemically depositing nanomaterials on the graphene layer on which the gold metal layer is formed; And

Cooling the graphene layer on which the gold metal layer on which the nanomaterial is chemically deposited is formed;

Including,

The gold metal layer is converted into an island structure upon chemical vapor deposition of the nanomaterial,

The nanomaterial is chemically deposited at 800 to 950 ° C. for 30 minutes to 2 hours,

The cooling is carried out at a rate of 10 to 100 ° C. per minute,

Forming a hybrid nanostructure in which nanowalls, a mixture of nanowalls and nanowires, and nanowires are mixed from the side close to the graphene layer on the graphene;

The nanomaterial is any one selected from the group consisting of group IV semiconductors, group III-V semiconductors, group II-VI semiconductors, group IV-VI semiconductors, group IV-V-VI semiconductors, nitride semiconductors, and metals. do.

According to another embodiment of the present invention, the graphene layer comprises the steps of growing a graphene layer by chemical vapor deposition on the metal catalyst layer; Removing the metal catalyst layer from the graphene layer; And transferring the graphene to a substrate.

According to another aspect of the present invention to achieve the second object,

Board;

A graphene layer formed on the substrate;

A hybrid nanostructure formed on the graphene layer and having a nanowall structure and a nanowire structure mixed therein; And

And a gold metal layer between the graphene layer and the nanostructure.

The hybrid nanostructure is a structure in which nanowalls, nanowalls and nanowires, and nanowires are formed from a substrate side,

The metal layer is 0.5 nm to 5 nm thick,

The nanostructure is any one nanomaterial selected from the group consisting of a group IV semiconductor, a group III-V semiconductor, a group II-VI semiconductor, a group IV-VI semiconductor, a group IV-V-VI semiconductor, a nitride semiconductor, and a metal. Composite nanostructures are provided.

According to another aspect of the present invention to achieve the third object, there is provided a nano-electric device comprising the composite nanostructure.

According to an embodiment of the present invention, by controlling the morphology of the nanostructures efficiently, a desired hybrid nanostructure may be formed on graphene to obtain a nano-electric device in DC mode.

1 is a view schematically showing a process for forming a hybrid nanostructure according to an embodiment of the present invention.
2 is a FE-SEM image photograph seen from above of the hybrid nanostructures prepared in Examples 1 to 3 of the present invention.
3 is a FE-SEM image photograph seen in cross section of the hybrid nanostructures prepared in Examples 1 to 3 of the present invention.
4 is an XRD graph of a composite nanostructure including the hybrid nanostructures prepared in Examples 1 to 3 of the present invention.
5 is a photograph of the analysis result of HR-TEM of the composite nanostructures including the hybrid nanostructures prepared in Example 2.
FIG. 6 is a graph showing the current density (FIG. 6A) and the voltage (FIG. 6B) over time of the nano-electric device including the hybrid nanostructures prepared in Example 2. FIG.
FIG. 7 is an HR-TEM image (FIG. 7A) and μ-EDS spectrum (FIG. 7B) of the hybrid nanostructures obtained in Example 2. FIG.

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

Method for forming a hybrid nanostructure on the graphene according to an embodiment of the present invention

Forming a graphene layer on the substrate;

Forming a gold metal layer on the graphene layer; And

And chemically depositing a nanomaterial on the graphene layer on which the gold metal layer is formed.

According to one embodiment of the present invention, by controlling the thickness of the gold metal layer acting as a catalyst for the growth of the nano-material to a certain range it is possible to effectively control the morphology of the nanostructures to form the desired hybrid nanostructures.

In the present invention, the term "hybrid nanostructure" means that nanostructures of various types such as nanowires, nanotubes, nanorods, and nanowalls are mixed, and in particular, nanostructures in which nanowalls and nanowires are mixed. Means.

In the present invention, "nanowire" means a structure that looks like a yarn having a diameter of several tens of nm to several hundred nm and a length of several micrometers to several tens of micrometers.

In the present invention, the term "nanowall" refers to a three-dimensional nanostructure having a three-dimensional structure, and refers to a wall structure vertically standing on the surface. That is, it means that the nanostructured walls are networked with each other to form a honeycomb shape.

1 is a process chart showing a method of forming a hybrid nanostructure according to an embodiment of the present invention. Hereinafter, a method of forming a hybrid nanostructure according to an embodiment of the present invention will be described in more detail with reference to FIG. 1.

First, the graphene layer 12 is formed on the substrate 11. The substrate 11 may be a transparent glass substrate, a plastic substrate, a metal oxide substrate, etc. without limitation, but may be a polyethylene naphthalate (PEN), SiO ₂ or Al ₂ O ₃ substrate.

The method of forming the graphene layer 12 on the substrate 11 can be used without any known method. For example, a carbon source is chemically deposited on a metal foil used as a graphitization catalyst to form graphene, and then PMMA is formed on the graphene opposite to the surface on which the graphitization catalyst is formed to transfer the graphene to a substrate. Spin coat the polymer. The etchant is then used to remove the graphitization catalyst, the graphene on PMMA is transferred onto the substrate, and then the solvent is used to remove PMMA.

Carbon may be supplied as a carbon source in the graphene formation process, and any material that may exist in the gas phase at a temperature of 300 ° C. or higher may be used without particular limitation. The gaseous carbon source may be a compound containing carbon, preferably a compound having 6 or less carbon atoms, more preferably a compound having 4 or less carbon atoms, and more preferably a compound having 2 or less carbon atoms. As such an example, one or more selected from the group consisting of carbon monoxide, methane, ethane, ethylene, ethanol, acetylene, propane, propylene, butane, butadiene, pentane, pentene, cyclopentadiene, hexane, cyclohexane, benzene and toluene can be used.

Such a carbon source may be introduced at a constant pressure in a chamber in which a graphitization catalyst is present, and only the carbon source may be present in the chamber, or may be present together with an inert gas such as helium, argon, or the like.

In addition, hydrogen may be used in addition to the carbon source. Hydrogen can be used to control the gas phase reaction by keeping the surface of the graphitization catalyst clean and can be used at 5-40% by volume of the total volume of the vessel, for example 10-30% by volume, or 15-25% by volume. .

The carbon source is introduced into a chamber in which a graphitization catalyst is present, and then heat-treated at a predetermined temperature to form graphene on the surface of the graphitization catalyst. The heat treatment is performed to maintain the film shape of the graphitization catalyst. The heat treatment temperature is an important factor in the production of graphene, for example, may be 300 to 2000 ℃, or 500 to 1500 ℃. When the heat treatment temperature is within the above range, it is possible to effectively obtain sheet-like graphene.

As described above, the heat treatment may be performed to maintain the graphene for a predetermined time at a predetermined temperature. That is, since the graphene is generated when the heat treatment process is maintained for a long time, the thickness of the resulting graphene can be increased. If the heat treatment process is shorter, the resulting graphene thickness is reduced. Therefore, in order to obtain a desired graphene thickness, in addition to the type and supply pressure of the carbon source, the type of graphitization catalyst, and the size of the chamber, the holding time of the heat treatment process may act as an important factor. The holding time of such a heat treatment process can generally be maintained for 0.001 to 1000 hours, if desired within the range can be effectively obtained the desired graphene.

As a heat source for the heat treatment, inducting heating, radiant heat, laser, IR, microwave, plasma, UV, surface plasmon heating and the like can be used without limitation. Such a heat source is attached to the chamber and serves to raise the inside of the chamber to a predetermined temperature.

After the heat treatment as described above, the heat treatment result is subjected to a predetermined cooling process. Such a cooling process is a process for allowing the produced graphene to grow uniformly and be uniformly arranged. Since rapid cooling may cause cracking of the produced graphene, it is preferable to cool it slowly at a constant speed as much as possible. For example, it can cool at a speed | rate of 10-100 degreeC per minute, and it is also possible to use methods, such as natural cooling. The natural cooling simply removes the heat source used for the heat treatment, and it is possible to obtain a sufficient cooling rate even by removing such a heat source.

Graphene obtained after such a cooling process may have a thickness ranging from one layer to about 300 layers, for example, may be 1 to 60 layers, or 1 to 15 layers.

The heat treatment and cooling process as described above may be performed in one cycle, but it is also possible to repeat the process several times to produce graphene having a high structure and high density.

The graphene layer may be formed by various methods such as reducing graphene oxide in addition to chemical vapor deposition.

The gold metal layer 13 may be formed on the graphene layer 12 by, for example, thermal evaporation. For example, the thickness of the gold metal layer to be formed may be adjusted to 0.5 nm to 5 nm.

As such, the hybrid nanostructure 15 is formed by chemically depositing the nanomaterial 14 on the graphene layer 12 having the gold metal layer 13 formed thereon.

In the conventional method, a nanomaterial layer is formed directly on a substrate or by spin coating on a graphene layer, a nanonucleus is formed by heating, and then the substrate is added to a solution in which the nanomaterial is dissolved to grow the nanomaterial. To form a nanostructure. In this case, it is possible to control the orientation of the nanostructure, but it is difficult to control the morphology of the nanostructure.

In addition, when a nanostructure is formed by directly growing a nanomaterial on a substrate by a vapor-liquid-solid method using a conventional gold metal layer, the nanomaterial and the substrate are formed rather than the binding energy between the gold and the substrate. As the bond energy of and is smaller, the nanostructures are pushed upwards. In this method, it is difficult to grow nanowires in a direction perpendicular to the substrate, and thus it is difficult to obtain a nano electric device having stable electrical characteristics.

In the present invention, a hybrid nanostructure having a desired morphology is obtained by forming and growing a nanomaterial by chemical vapor deposition using a gold metal layer as a catalyst on a graphene layer.

The hybrid nanostructure 15 may be arranged from the substrate 11 side to the nanowall 16, the mixture 17 of nanowalls and nanowires, and nanowires 18. That is, the nanomaterials grow in the form of nanowalls by the gold metal layer, and as the distance from the gold metal layer increases, the nanowires begin to grow and finally form a nanowire structure. In addition, the nanowires are arranged completely perpendicular (002) on the graphene surface.

In the method of growing a nanomaterial according to an embodiment of the present invention, for example, a graphene layer in which a gold metal layer is present is placed in a chamber, and zinc oxide and graphite powder are chemically deposited on the graphene layer under an inert gas atmosphere. To form and grow nanomaterials. Raw powders such as GaN, VO ₂ , SnO ₂ , CdS, CdSe, and TiO ₂ may be used depending on the type of nanomaterial formed on the graphene layer by chemical vapor deposition. The chemical vapor deposition may be performed at 800 to 950 ° C. for 30 minutes to 2 hours.

During the chemical vapor deposition, the gold metal layer forms an island structure by heat, and the island structure acts as a nucleation site to grow nanomaterials. That is, when heat is applied to the deposited gold metal layer, it is changed into a spherical island to reduce surface energy. In general, a gold metal thin film deposited with a thickness of nano units is transformed into an island shape at about 350 to 800 ° C. In addition, in the case of the island structure of gold, when the thickness of the gold metal layer is increased, the size and density of the island structure are increased. A hybrid nanostructure may be formed on the gold metal layer of the island structure. The hybrid nanostructure is a mixture of nanowalls and nanowires, and nanowalls, a mixture of nanowalls and nanowires, and nanowires may be mixed from a side close to the graphene layer.

When the nanomaterial is grown directly on a conventional substrate, the substrate is damaged due to a high growth temperature, but in the present invention, the graphene buffer layer is present on the substrate to prevent damage to the substrate.

In addition, when the nanomaterial is grown on the graphene layer as in the present invention, the binding energy of the gold metal and the graphene is smaller than the binding energy of the nanomaterial and the graphene, so that the gold metal covalently bonds with the graphene and is stably nano. In addition to the formation of structures, the presence of gold is advantageous in the manufacture of optical devices due to the surface plasmon effect.

When explaining the principle of obtaining a hybrid nanostructure by adjusting the thickness of the gold metal layer as in the present invention, it is as follows, which is for the purpose of explanation only, but not limiting the present invention.

The diffusion coefficient of the gold metal particles forming the island structure may be represented by Equation 1 below:

[Equation 1]

In other words, the diffusion coefficient D is related to the activation energy Ea required for the gold atom to jump.

By controlling the chemical vapor deposition temperature range of the nanomaterial to 800 to 950 ℃, it is possible to suppress the diffusion to the graphene surface of the gold atom to form a strong covalent bond between the carbon atom and the gold in the graphene network. In addition, the nanostructures formed thereon also have a morphology controlled according to the size of the diffusion coefficient to form a hybrid nanostructure. In particular, when the chemical vapor deposition in the above temperature range, the nanowall structure is formed on the gold metal particles to a certain height, then a mixture of nanowalls and nanowires, and nanowires are sequentially formed.

As the deposition temperature is increased, the gold metal islands formed on the graphene have a relatively uniform distribution. Part of the gold metal is also distributed in the grain boundaries of graphene. Accordingly, by controlling the thickness of the gold metal layer, it is possible to control the shape of the nanostructures formed thereon. As the thickness of the gold metal layer becomes thicker, the density and size of the gold metal islands increase, and accordingly, each nano Nanostructures in the form of structures are formed.

For example, as the thickness of the deposited gold metal layer increases from 0.5 nm to 1 nm, the nanostructures increase in volume due to alloy formation with gold metal islands, and nanowalls are formed by network phenomenon with surrounding gold metal islands. Then, after nanowalls grow to a certain height, nanowires begin to form, and nanowalls, a mixture of nanowires, and nanowires are sequentially formed to ultimately form hybrid nanostructures.

Meanwhile, upon chemical vapor deposition of nanomaterials, the gold metal layer forms an island structure, and the island structure is formed along the grain boundary of graphene. In other words, graphene has many grain boundaries, which have an unstable energy state at the interface where each single crystal meets. The island structure of the gold metal is vibrated and moved while being transformed into a shape having a low energy shape by thermal energy, and is located at an energy unstable grain boundary. Therefore, since the grain size of the graphene can be determined by measuring the average diameter of the island structure of the gold metal, an appropriate crystallization condition of the graphene can be set.

The nanomaterial used in the method according to an embodiment of the present invention is a group IV semiconductor, such as C, Si, Ge, group III-V semiconductor, group II-VI semiconductor, group IV-VI semiconductor or IV-V-VI It may be made of a group semiconductor, etc. In addition, it may be made of an oxide semiconductor, a nitride semiconductor or a metal such as ZnO. However, the nanomaterial is not limited thereto, and may be made of various materials. Meanwhile, the nanomaterial may have a heterostructure in which materials having different components are combined, for example, a heterostructure in the radial direction or a heterostructure in the longitudinal direction.

According to another aspect of the invention, the substrate; A graphene layer formed on the substrate; And a hybrid nanostructure formed on the graphene layer and including a hybrid nanostructure in which a nanowall structure and a nanowire structure are mixed.

The composite nanostructure may further include a gold metal layer between the graphene layer and the hybrid nanostructure.

In the composite nanostructure, the hybrid nanostructure may have a nanowall, a mixture of nanowalls and nanowires, and nanowires mixed from the graphene layer.

According to still another aspect of the present invention, a nano electric device including the composite nanostructure is provided.

The nano electric device may further include a counter electrode layer spaced apart from the composite nanostructure. The counter electrode layer may be any material used as a general electrode such as graphene layer, ITO, Au or Pt, IZTO.

In the nano-electric device, the substrate may be a transparent polyethylene terephthalate (PEN), SiO ₂ or Al ₂ O ₃ substrate.

Nano electric device according to an embodiment of the present invention may be a nano generator having a DC (Direct Current) mode.

When a force is applied to the nanostructure constituting the nano-electric device, the electrons on the nanostructure move to the lower portion of the nanostructure, and in the case of the nanostructure consisting of only nanowires, the force is removed and the electrons existing on the nanostructure under the nanostructure again The nanogenerator in AC mode is achieved. However, when the nanowall is present in the lower portion of the nanostructure as in the present invention, since the electrons that have moved do not accumulate and flow back to the upper portion of the nanostructure, it is possible to form a nano-mode generator in DC mode.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

Example 1

Preparation of Graphene Sheet on Substrate

Cu foil (purchased by Wacopa thickness: 0.2T) was placed in a chamber (manufacturer: Keptek, Model: High Temp.Furnace 14030FL), and the mixed gas (methane: hydrogen = 2: 1) was placed at 30 sccm in the chamber. Heat treatment at 1000 ° C. for 30 minutes using a halogen lamp heat source with constant dosing in it produced graphene on the Cu foil.

Subsequently, a chlorobenzene solution (5 wt%) in which PMMA was dissolved on the graphene / Cu foil was coated for 60 seconds at a speed of 1,000 rpm to separate the graphene from the Cu foil, and the resultant was then etchant (CuSO ₄ + HCl). + FeCl) solution (purchased from TRANSENE COMPANY Inc., product name: Nickel Etchant type 1). The graphene attached to the PMMA was separated by immersing for 1 hour to remove the Cu foil. The graphene attached on the PMMA was transferred to the sheet in an Al ₂ O ₃ layer and dried, and then the PMMA was removed with acetone. This transfer process was repeated three times to obtain a graphene 3 layer.

Graphene / Al ₂ O ₃ Gold (Au) metal layer on top (thickness 0.5nm)

In the bottom of the thermal evaporation equipment (manufacturer: Sntek) chamber, a gold metal (source) was charged and a graphene / Al ₂ O ₃ substrate was mounted on the top. After mounting the substrate and the source, the interior of the chamber passed through low vacuum (1 × 10 ⁻³ torr) to high vacuum (1 × 10 ⁻⁵ torr). The gold metal was vaporized by applying heat to the underlying gold metal in a high vacuum atmosphere, and the vaporized gold gas was deposited on a graphene / Al ₂ O ₃ substrate. The thickness of the gold metal layer formed was adjusted to 0.5 nm using a sensor monitor mounted on the thermal evaporation method equipment.

ZnO Hybrid Nanostructure Formation

A powder mixed with zinc oxide and graphite was charged in the center of the chamber, and the prepared gold / graphene / Al ₂ O ₃ substrate was positioned about 1 cm away from the mixed powder. When the mixing powder and the setting of the substrate in the chamber were completed, the temperature was increased in an inert gas atmosphere (Ar gas, feed flow rate 1000 sccm). At this time, the chemical vapor deposition was carried out for about 60 minutes at 900 ℃.

Example 2

A ZnO hybrid nanostructure was formed in the same manner as in Example 1, except that the thickness of the gold metal layer was 1.0 nm instead of 0.5 nm in Example 1.

Example 3

A ZnO hybrid nanostructure was formed in the same manner as in Example 1, except that the thickness of the gold metal layer was 2.0 nm instead of 0.5 nm in Example 1.

FIG. 2 shows a FE-SEM photograph seen from above of the hybrid nanostructures grown according to Examples 1-3. FIG.

Figure 3 shows the FE-SEM picture from the cross-section of the hybrid nanostructures grown in accordance with Examples 1 to 3.

2 and 3, it can be seen that the morphology of the hybrid nanostructures according to the embodiment of the present invention depends on the thickness of the gold metal layer. In other words, the thicker the thickness of the gold metal layer, the larger the size of the island structure of gold, and the larger the diameter of the nanostructures grown thereon. It can be seen formed. However, it can be seen that the hybrid nanostructures prepared in Examples 1 to 3 all have the shape of nanowalls, mixtures of nanowalls and nanowires, and nanowires from the graphene layer.

Figure 4 shows the XRD pattern of the hybrid nanostructures obtained according to Examples 1 to 3 of the present invention. As shown in Figure 4, it can be seen that the nanowires of the hybrid nanostructures according to the embodiment of the present invention are grown in the vertical direction (002) with respect to the graphene layer. In other words, the method for forming a hybrid nanostructure according to an embodiment of the present invention allows to obtain a nano electric device having stable electrical properties by controlling the growth direction of the nanowires in a direction perpendicular to the substrate.

5 is a diagram showing an HR-TEM image of a hybrid nanostructure grown according to Example 2 of the present invention.

As shown in FIG. 5, it can be seen that graphene is present on the Al ₂ O ₃ substrate, and the ZnO hybrid structure grown thereon can be confirmed. In addition, it can be seen that ZnO is grown in the same direction as the 002 direction of graphene growth.

On the other hand, using the nanostructures obtained in Examples 1 to 3 and Comparative Example 1 and Comparative Example 2 to prepare a nano-electric device.

The nano electric device was fixed to the upper substrate and the lower substrate by using a glue gun equipment, and the wires were used at the upper and lower electrodes to connect to the measuring equipment. The paste was used to bond the wires and the electrodes. The overall structure of the device is in the form of an Al ₂ O ₃ substrate and graphene // ZnO hybrid nanostructure // gold metal layer // flexible substrate.

Switching polarity test was performed using the nano-electric device manufactured above. The switching polarity test determines whether the electric device is driven. That is, the signal output from the electric element is a very low unit, and is to determine whether the output value to be measured is introduced from outside or measured by driving the device. The switching polarity test method determines whether the output direction of the device is changed when the polarity of the device is changed during the measurement.

6 is a view showing a switching polarity test of the nano-electric device manufactured according to Example 2 of the present invention.

As shown in Figure 6, it was possible to confirm the current density and voltage of the DC type.

FIG. 7 is a diagram showing HR-TEM images and μ-EDS spectra of nanostructures grown according to Example 2 of the present invention. As shown in Figure 7, it can be seen that the position of Au (metal catalyst) is located on the graphene.

In one embodiment of the present invention by controlling the morphology of the hybrid nanostructure by the thickness of the gold metal layer to a certain range it can be obtained a nano-electric device having a stable electrical properties and DC mode.

11: substrate 12: graphene layer
13: gold metal layer 14: nanomaterial
15: nanostructure 16: nanowall
17: Mixture of nanowalls and nanowires
18: Nanowire

Claims (9)

Forming a graphene layer on the substrate;
Forming a gold metal layer on the graphene layer;
Chemically depositing nanomaterials on the graphene layer on which the gold metal layer is formed; And
Cooling the graphene layer on which the gold metal layer on which the nanomaterial is chemically deposited is formed;
Including,
The gold metal layer is converted into an island structure upon chemical vapor deposition of the nanomaterial,
The nanomaterial is chemically deposited at 800 to 950 ° C. for 30 minutes to 2 hours,
The cooling is carried out at a rate of 10 to 100 ° C. per minute,
Forming a hybrid nanostructure in which nanowalls, a mixture of nanowalls and nanowires, and nanowires are mixed from the side close to the graphene layer on the graphene;
The nanomaterial is any one selected from the group consisting of a group IV semiconductor, a group III-V semiconductor, a group II-VI semiconductor, a group IV-VI semiconductor, a group IV-V-VI semiconductor, a nitride semiconductor, and a metal. The method of claim 1,
Growing the graphene layer by chemical vapor deposition on the metal catalyst layer;
Removing the metal catalyst layer from the graphene layer; And
Transferring the graphene to a substrate. The method of claim 1,
The metal layer is formed to a thickness of 0.5nm to 5nm. Board;
A graphene layer formed on the substrate;
A hybrid nanostructure formed on the graphene layer and having a nanowall structure and a nanowire structure mixed therein; And
And a gold metal layer between the graphene layer and the nanostructure.
The hybrid nanostructure is a structure in which nanowalls, nanowalls and nanowires, and nanowires are formed from a substrate side,
The metal layer is 0.5 nm to 5 nm thick,
The nanostructure is any one nanomaterial selected from the group consisting of a group IV semiconductor, a group III-V semiconductor, a group II-VI semiconductor, a group IV-VI semiconductor, a group IV-V-VI semiconductor, a nitride semiconductor, and a metal. Composite nanostructures. The method of claim 4, wherein
The substrate is a transparent polyethylene naphthalate (PEN), SiO ₂ or Al ₂ O ₃ substrate composite nanostructure. A nanoelectric device comprising the composite nanostructure of claim 4. The method of claim 6,
And a counter electrode layer spaced apart from each other on the hybrid nanostructure. The method of claim 7, wherein
The counter electrode layer is a graphene layer, ITO, AU, Pt or IZTO nano electric device. The method of claim 6,
The nano electric device is a direct current (DC) mode nanogenerator.

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