KR101772675B1 - N-doped graphene oxide/graphene bilayer structure and preparing method of the same - Google Patents
N-doped graphene oxide/graphene bilayer structure and preparing method of the same Download PDFInfo
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- KR101772675B1 KR101772675B1 KR1020150087158A KR20150087158A KR101772675B1 KR 101772675 B1 KR101772675 B1 KR 101772675B1 KR 1020150087158 A KR1020150087158 A KR 1020150087158A KR 20150087158 A KR20150087158 A KR 20150087158A KR 101772675 B1 KR101772675 B1 KR 101772675B1
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- C01B32/186—Preparation by chemical vapour deposition [CVD]
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
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- C23C16/26—Deposition of carbon only
Abstract
Layer structure of N-doped graphene oxide / graphene and a process for producing the double-layer structure of N-doped graphene oxide / graphene.
Description
The present invention, Layer structure of N-doped graphene oxide / graphene and a process for producing the double-layer structure of N-doped graphene oxide / graphene.
Graphene is a transparent two-dimensional material that has excellent electrical conductivity, is thermally / chemically stable, is very flexible, and transmits about 97.7% of the wavelength in the visible light region. In addition, much attention has been focused on the doping of graphenes because the adjustable electrical properties of graphene can be achieved by doping.
Among methods for using graphene as a transparent electrode, there is an effect of lowering the resistance by using a method of laminating graphene as several layers, but this method has a problem in that the transmittance is reduced.
On the other hand, graphene oxide is difficult to obtain as a single layer and is not suitable for use as a transparent electrode due to its opaque property when it is produced by a generally known Hummer's method. As another alternative, the conventional doping methods, such as silicon, have a problem of replacing nitrogen or boron at the carbon sites, but changing the properties of the graphene structure by destroying the structure.
Accordingly, it is required to develop a method capable of improving both the transparent property and the electrical property of graphene. Korean Patent Publication No. 2012-0099910 discloses an n-doping method of graphene.
The present application is intended to provide a dual layer structure of N-doped graphene oxide / graphene and a method of producing the double-layer structure of N-doped graphene oxide / graphene.
However, the problems to be solved by the present invention are not limited to the above-mentioned problems, and other problems not mentioned can be clearly understood by those skilled in the art from the following description.
According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming graphene oxide by oxygen-plasma treatment of a first graphene; Forming a bilayer structure of graphene oxide / graphene by transferring the graphene oxide onto a second graphene; And doping the bilayer structure of the graphene oxide / graphene with an amine-containing functional group.
A second aspect of the present application is a process for preparing a graphene oxide / graphene bilayer structure comprising a bilayer structure of graphene oxide / graphene prepared by the method according to the first aspect and doped with amine-containing functional groups, Layer structure of N-doped graphene oxide / graphene, which is transparent.
In one embodiment of the present invention, the formation of graphene oxide by oxygen-plasma treatment oxidizes graphene under a soft condition, which is effective to form a transparent monolayer of graphene oxide.
The double layered structure of N-doped graphene oxide / graphene according to one embodiment of the present invention maintains improved electrical characteristics and high transparency when used as an electrode, exhibits a strong N-doping effect, and is used as a transparent electrode Lt; / RTI >
The bilayer structure of the N-doped graphene oxide / graphene according to one embodiment of the present invention is such that the amine-containing functional groups chemically bond to the graphene oxide to form a self-assembled layer, The effect can be sustained.
In the double-layer structure of N-doped graphene oxide / graphene according to an embodiment of the present invention, the graphene layer as a conductive layer and the graphene oxide layer as a doping layer are all bent over and bent over 20,000 times The characteristics can be maintained.
In one embodiment of the present invention, the bilayer structure of the N-doped graphene oxide / graphene can convert the amine to ammonium ion through protonation and as a result, the graphene oxide / May be P-doped, but the present invention is not limited thereto. In addition, the double layered structure of the P-doped graphene oxide / graphene can be regenerated as a double layer structure of the N-doped graphene oxide / graphene by deprotonating again. The change in the characteristics of the graphene due to the surface change is sufficient to be used as a sensor in the future.
In one embodiment of the present invention, the double layered structure of the N-doped graphene oxide / graphene is excellent in thermal stability and can be used as a flexible transparent electrode material because of its flexibility and transparency.
1 is a schematic diagram illustrating a method for producing a double layer structure of N-doped graphene oxide / graphene according to one embodiment of the present invention.
FIG. 2 is a graph of an electrical characteristic test result of the structures according to an embodiment of the present invention.
FIG. 3 is a spectrum of experimental results of X-ray photoelectron spectroscopy of structures according to an embodiment of the present invention.
4 is a Raman spectroscopic experimental result spectrum of structures according to an embodiment of the present invention.
FIG. 5 is a graph showing the experimental results of light transmittance of structures according to an embodiment of the present invention.
FIG. 6 is a graph of experimental results of high-temperature stability of structures according to an embodiment of the present invention.
7 is a graph of the flexibility test of structures according to one embodiment of the present application.
FIG. 8 is a graph showing the results of the experiment for the positive / negative control of structures according to one embodiment of the present invention.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. It should be understood, however, that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.
Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.
Throughout this specification, when a member is "on " another member, it includes not only when the member is in contact with the other member, but also when there is another member between the two members.
Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.
The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure.
The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.
Throughout this specification, the term "combination (s) thereof " included in the expression of the machine form means a mixture or combination of one or more elements selected from the group consisting of the constituents described in the expression of the form of a marker, Quot; means at least one selected from the group consisting of the above-mentioned elements.
Throughout this specification, the description of "A and / or B" means "A or B, or A and B".
Throughout this specification, the term "graphene (Gr)" means that a plurality of carbon atoms are covalently linked to one another to form a polycyclic aromatic molecule, wherein the carbon atoms linked by the covalent bond 6 membered ring, but it is also possible to further include a 5-membered ring and / or a 7-membered ring.
Throughout the present specification, the term "graphene oxide" may be abbreviated as "GO" and refers to a structure in which a functional group containing oxygen such as a carboxyl group, a hydroxyl group, or an epoxy group is bonded on a single layer graphene But are not limited thereto.
As used herein, unless otherwise specified, the term "alkyl ", alone or in combination with another term such as" alkoxy "and" alkylamino & Or a linear or branched radical having from about 1 to about 20 carbon atoms, or from about 1 to about 10 carbon atoms, or from about 1 to about 6 carbon atoms. Alternatively, from about 1 to about 20 carbon atoms, or from about 1 to about 10 carbon atoms, or alkyl groups may be substituted at any carbon position by other substituents. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, isohexyl, heptyl, 4-trimethylpentyl, nonyl, decyl, undecyl, dodecyl, and isomers thereof, but are not limited thereto.
Throughout this application, the term "alkoxy ", alone or as part of another group, refers to an alkyl group as described above bonded via an oxygen linkage (-O-).
Hereinafter, embodiments of the present invention are described in detail, but the present invention is not limited thereto.
According to a first aspect of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: forming graphene oxide by oxygen-plasma treatment of a first graphene; Forming a bilayer structure of graphene oxide / graphene by transferring the graphene oxide onto a second graphene; And doping the bilayer structure of the graphene oxide / graphene with an amine-containing functional group. The formation of the graphene oxide by the oxygen-plasma treatment is effective in oxidizing graphene under a soft condition, so that a transparent single-layer graphene oxide can be formed.
In one embodiment of the present invention, the first graphene and the second graphene may be formed by chemical vapor deposition, but the present invention is not limited thereto. Non-limiting examples of the chemical vapor deposition method include rapid thermal chemical vapor deposition (RTCVD), inductively coupled plasma-chemical vapor deposition (ICP-CVD), low pressure chemical vapor deposition such as low pressure chemical vapor deposition (LPCVD), atmospheric pressure chemical vapor deposition (APCVD), metal organic chemical vapor deposition (MOCVD), or plasma-enhanced chemical vapor deposition deposition (PECVD), but may not be limited to these.
In one embodiment of the present invention, the first graphene and the second graphene may be formed on a substrate, but the present invention is not limited thereto. For example, the substrate may be selected from the group consisting of silica, Ge, Ni, Co, Fe, Pt, Au, Al, Cr, Cu, Mg, Mn, Mo, Rh, Si, Ta, Ti, W, but are not limited to, those selected from the group consisting of brass, bronze, white brass, stainless steel, and conductive transparent substrates. The conductive transparent substrate may be, but not limited to, those used in the art.
In one embodiment of the invention, the transfer of the graphene oxide onto the second graphene may be by a wet transfer method, but is not limited thereto. For example, the wet transfer may include transferring gold using a polymer (e.g., polymethyl methacrylate, polybutadiene) after depositing gold on the surface of the graphene oxide, but not limited thereto .
In one embodiment herein, doping with the amine-containing functional group can be performed using (3-aminopropyl) triethoxysilane, tridecafluoro-N-octyltriethoxysilane tridecafluoro-N-octyltriethoxysilane, N-octyltriethoxysilane, p-aminophenyltrimethoxysilane, aminotriethoxysilane, N- (2-amino 3-aminopropyltrimethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine], N- (2-aminoethyl) (Trimethoxysilylpropyl) ethylenediamine triacetic acid], and combinations thereof. [0040] The term " acid addition salt " have.
In one embodiment of the present invention, the first graphene and the second graphene may each be a single layer, but the present invention is not limited thereto. The bilayer structure of the N-doped graphene oxide / graphene formed according to the present invention formed thereafter may have high transparency, but may not be limited thereto.
In one embodiment of the present invention, the N-doping method of the graphene can be performed at least once, but the present invention is not limited thereto. Thus, a laminate of the N- doped graphene oxide / Can be produced.
In one embodiment of the present invention, the step of doping the bilayer structure of graphene oxide / graphene with the amine-containing functional group comprises the step of doping the graphene oxide / But may be, but not limited to, immersing the bilayer structure.
In one embodiment herein, the amine-containing functional groups may be doped by being self-assembled on the graphene oxide layer, but may not be limited thereto. Accordingly, the double-layer structure of N-doped graphene oxide / graphene according to one embodiment of the present invention is formed at a temperature of about 200 < 0 > C, because the amine-containing functional groups chemically bond to the graphene oxide layer to form a self- The doping effect can be maintained even at high temperatures.
In one embodiment of the present invention, the method may further include a step of heat-treating the double-layer structure of graphene oxide / graphene in a vacuum atmosphere before and after doping with the amine-containing functional group, But may not be limited. The heat treatment in the vacuum atmosphere may be performed, for example, at a temperature ranging from about 50 캜 to about 200 캜, but may not be limited thereto. The heat treatment in the vacuum atmosphere may be performed at a temperature of, for example, about 50 캜, about 75 캜, about 100 캜, about 120 캜, or about 150 캜.
In one embodiment of the present invention, the step of heat-treating in a vacuum atmosphere before doping may have an effect of removing interlayer impurities of graphene oxide / graphene bilayer structure, but may not be limited thereto.
In one embodiment, the step of heat-treating in a vacuum atmosphere after doping may have the effect of removing the unreacted (un-doped) amine-containing functional groups and completing the doping structure, but is not limited thereto .
In one embodiment herein, the step of doping the bilayer structure of graphene oxide / graphene with the amine-containing functional groups may include, but is not limited to, being performed in an argon atmosphere .
In one embodiment of the present invention, the step of doping the bilayer structure of graphene oxide / graphene with the amine-containing functional group may be performed by a catalytic reaction, but may not be limited thereto. The catalyst may be, for example, but not limited to, N, N'-dicyclohexyl-carbodiimide.
In one embodiment herein, the step of doping the bilayer structure of graphene oxide / graphene with the amine-containing functional groups may be performed at a temperature ranging from about 50 ° C. to about 100 ° C., But may not be limited. For example, the doping step may be performed at a temperature of about 75 DEG C, but may not be limited thereto.
In one embodiment of the invention, the doping may be performed by moving lone-pair electrons of the amine-containing functional group to the graphene layer, but may not be limited thereto, The graphene oxide layer may serve as an intermediary for transferring the electrons to the graphene layer, but may not be limited thereto.
The N-doping method of graphene according to one embodiment of the present invention is shown in FIG.
A second aspect of the present application is a process for preparing a graphene oxide / graphene bilayer structure comprising a bilayer structure of graphene oxide / graphene prepared by the method according to the first aspect and doped with amine-containing functional groups, Layer structure of N-doped graphene oxide / graphene, which is transparent. All of the descriptions of the graphene N-doping method of the first aspect of the present invention can be applied to the double-layer structure of N-doped graphene oxide / graphene according to this aspect.
In one embodiment herein, the amine-containing functional group is selected from the group consisting of (3-aminopropyl) triethoxysilane, tridecafluoro-N-octyltriethoxysilane, octyltriethoxysilane, N-octyltriethoxysilane, p-aminophenyltrimethoxysilane, aminotriethoxysilane, N- (2-aminoethyl) -3- (2-aminoethyl) -3-aminopropyltrimethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, N- (trimethoxysilylpropyl) diethylenetriamine, But are not limited to, those selected from the group consisting of ethylenediamine triacetic acid, N- (trimethoxysilylpropyl) ethylenediamine triacetic acid, and combinations thereof.
In one embodiment of the invention, the bilayer structure of graphene oxide / graphene doped with the amine-containing functional groups may be formed on a substrate, for example, the substrate may be silica, Ge, Ni, Co Ti, W, U, V, Zr, brass, bronze, white brass, and the like. , Stainless steel, and a conductive transparent substrate, but the present invention is not limited thereto. The conductive transparent substrate may be, but not limited to, those used in the art.
The graphene oxide layer and the graphene layer of the double-layer structure of the N-doped graphene oxide / graphene according to an exemplary embodiment of the present invention may each be a single layer and thus have high transparency, .
In one embodiment of the present invention, the bilayer structure of the N-doped graphene oxide / graphene may include one or more double layers (N-GO / Gr) of N-doped graphene oxide / However, the present invention is not limited thereto.
The bilayer structure of the N-doped graphene oxide / graphene according to an embodiment of the present invention may be used as a transparent element, for example, as a conductive transparent electrode, but may not be limited thereto.
In one embodiment of the present invention, the bilayer structure of the N-doped graphene oxide / graphene can convert the amine to ammonium ion through protonation and as a result, the graphene oxide / May be P-doped, but the present invention is not limited thereto. In addition, the double layered structure of the P-doped graphene oxide / graphene can be regenerated as a double layer structure of the N-doped graphene oxide / graphene by deprotonating again. Depending on the change in the surface charge of the graphene, the N-doped graphene oxide / graphene bilayer structure according to one embodiment of the present invention may be used as a sensor, but the present invention is not limited thereto. The sensor may be, but is not limited to, a pH sensor, for example.
In one embodiment of the present invention, the double layered structure of the N-doped graphene oxide / graphene is excellent in thermal stability and can be used as a flexible transparent electrode material because of its flexibility and transparency.
Hereinafter, the present invention will be described in more detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
[ Example ]
Example 1: N- Doped Grapina Oxide / Grapina Double layer Fabrication of Structures
A single layer of the first graphene prepared by chemical vapor deposition on a Ge substrate was oxidized by oxygen-plasma treatment through a very soft condition to form a transparent monolayer of graphene oxide. On the other hand, a second graphene was formed on the SiO 2 / Si substrate by chemical vapor deposition. After depositing gold on the surface of the prepared graphene oxide, the graphene oxide was deposited on the SiO 2 / Si substrate using a polymethyl methacrylate (PMMA) polymer using a wet transfer method. And transferred onto a second graphene to form a bilayer structure of graphene oxide / graphene. Thereafter, heat treatment was performed in a vacuum atmosphere at a temperature of 120 ° C to remove interlayer impurities.
(3-aminopropyl) triethoxysilane (3-aminopropyl) triethoxysilane, which is an amine-containing functional group, contained in the graphene oxide in the bilayer structure of graphene oxide / , APTES], a graphene oxide / graphene bilayer with an N, N-dicyclohexyl-carbodiimide catalyst was immersed in an APTES solution in an argon atmosphere and then maintained at 75 ° C for 12 hours. After the self-assembled layer of APTES was formed on the graphene oxide, unreacted APTES was removed and heat treatment was performed in a vacuum atmosphere at a temperature of 150 ° C to complete the doping structure.
[ Experimental Example ]
A field-effect transistor including the double-layer structure of the N-doped graphene oxide / graphene of Example 1 was fabricated to observe whether the doping was performed well and the electrical characteristics were observed.
A method of manufacturing a field effect transistor is as follows. First, a gold film of 40 nm was formed on the graphene formed on the copper by the chemical vapor deposition method by the thermal vapor deposition method. Then, polymethylmethacrylate (PMMA) was coated at a speed of 2,000 rpm for about 35 seconds using a spin coater. On the other hand, a self-assembled layer of octadecyltrichlorosilane (OTS) was formed on silicon dioxide / silicon [SiO 2 (300 nm) / Si] to be used as a substrate of the transistor. This is to prevent charge scattering occurring between the graphene and the substrate. The graphene, which is a conducting layer, was selectively transferred onto the transistor substrate using a thermal release tape (TRT). Treated at a temperature of 120 DEG C in a vacuum environment so that the graphene, which is the conductive layer, and the substrate on which the self-assembled layer (OTS) are formed can be adsorbed well. Meanwhile, graphene formed on copper was oxidized using oxygen-plasma to prepare graphene oxide. The graphene oxide, which is a doping layer, was deposited by gold film deposition and polymethylmethacrylate as in the case of the graphene. The polymethylmethacrylate of graphene on the heat treated substrate for about 2 hours was immersed in acetone to remove it and immersed in KI / I 2 solution to dissolve the gold. Then, the graphene oxide, which is a doping layer, was transferred to the surface of the graphene which is a conductive layer through wet-transfer to prepare a graphene oxide / graphene bilayer structure. And annealed at 120 DEG C for 12 hours in a vacuum oven so that adsorption between the two interfaces is well performed. After removing the polymethylmethacrylate by immersing in acetone, AZ5214E, a photoresist (PR), was spin-coated. After patterning using a photolithographic method, KI / I 2 The solution was immersed in the solution except for the pattern immersed in the solution. Thereafter, the photoresist layer was immersed in acetone to remove the photoresist layer, and then the graphene oxide / graphene layer except the pattern was removed using reactive ion etching (RIE). Photolithography was repeated once again. (3-aminopropyl) triethoxysilane ((3-aminopropyl) triethoxysilane), which is an amine-containing functional group, contained in the graphene oxide in the bilayer structure of the graphene oxide / -aminopropyl) triethoxysilane (APTES), graphene oxide / graphene double layer was immersed in an APTES solution together with N, N-dicyclohexylcarbodiimide catalyst in an argon atmosphere, and then reacted at 75 DEG C for 12 hours . After the formation of the self-assembled layer on the graphene oxide, unreacted APTES was removed and heat treatment was performed in a vacuum atmosphere at 150 캜 to complete the doping structure.
Samples for comparison were also used as comparative examples. The comparative example is a structure [GOGr] in which pure graphene [Gr], graphene oxide [GO] and graphene oxide (GO) are stacked as a conductive layer and / or a doped layer on a graphene (Gr) Are structures made by doping compounds.
1) Sheet resistance measurement
In the present embodiment, the sheet resistance of the field effect transistor manufactured in the above Experimental Example was measured through a 4-probe measurement using an MSTECH MST5000 Keithley SCS-4200 instrument.
As shown in FIG. 2, when graphene oxide (GO) contains a structure (GOGr / OTS-SiO 2 ) (blue line) in which graphene (GO) is laminated on graphene There was a slight P-doping effect compared to using [Gr / OTS-SiO 2 ] (black line). However, when a double layered structure of N-doped graphene oxide / graphene according to the present embodiment is included, the charge neutral point of [AGOGr / OTS-SiO 2 ] is found to be very leftward, which is due to N-doping You can check (red line). In this experiment, the lone-pair electron of the nitrogen of the amine group is transferred to the graphene, so that the N-type is doped and the charge neutral point is also shifted to the left.
Since the self-assembled layer containing amine groups in graphene oxide is bonded at a very high density, it transfers a large amount of electrons to the graphene, resulting in a very strong N-doping property.
2) x-ray photoelectron spectroscopy
The degree of surface doping was checked by x-ray spectroscopy. In this example, X-ray photoelectron spectroscopy was analyzed using an ESCA2000 using monochromatic instrument.
Referring to FIG. 3, it can be seen that the peak of oxygen in graphene oxide [GO] treated with oxygen plasma is stronger than that of graphene [Gr] among the surfaces of each sample. In addition, the surface [AGO] of the N-doped graphene oxide / graphene bilayer structure according to the present embodiment subjected to N-doping treatment exhibits nitrogen and silicon peaks due to the functional groups attached to the ends of the double layer reacted with APTES Respectively.
3) Raman spectroscopy
It was confirmed that graphene oxide was effectively formed and N-doped through the change of peak position and intensity of Raman spectroscopy. In this embodiment, Raman spectroscopy experiments were performed using a Raman system with excitation wavelength of 532 nm (2.33 eV) by WITEC.
As shown in FIG. 4, graphene [Gr] was graphene oxide, which greatly increased D peak and decreased 2D peak after [GO] oxidation. When this was physically transferred to produce a graphene oxide / graphene bilayer structure [GO / Gr], a structure having functional groups capable of doping was formed while maintaining electrical conductivity. It can be confirmed that N-doping is effectively performed by shifting the position of G peak in [AGO / Gr] after N-doping according to this embodiment.
4) UV-Vis measurement
Visibility of the double-layer structure of N-doped graphene oxide / graphene according to the present example was confirmed through UV-Vis with other comparative examples as to whether the double layer structure still retains transparency even after N-doping. In this embodiment, the transmittance in air was analyzed using a UV3600 instrument manufactured by SHIMADZU. As shown in FIG. 5, through the measurement of transmittance according to the lamination, the possibility of using the double-layer structure of this embodiment as a transparent electrode was confirmed. Here, when graphene oxide was used, the transmittance was increased, which was confirmed to be a result of the breakage of the graphene structure in GO formation. As the Fermi level became higher after the doping of the bilayer structure of the present example, the transmittance was improved by the band structure of the graphene changed and the possibility of the use of the transparent electrode was confirmed. In addition, the samples multiple layer laminate such a structure (4 th, 5 th, 6 th) to Despite research results laminating yeoryeo layer of six layer (AGO / Gr / AGO / Gr / AGO / Gr; 6 th ), It was confirmed that the transparency was 90% or more, which was very transparent.
4) High temperature stability measurement
In the present embodiment, the MSTECH MST5000 Keithley SCS-4200 instrument is used to determine whether the self-assembled layer containing amine groups is stable at high temperature through a 4-probe measurement I checked. As shown in Fig. 6, it was confirmed that there was almost no change in resistance even at a relatively high temperature of 220 占 폚. This is because amine molecules are chemically bonded to graphene rather than physically adsorbed. This indicates the possibility of being able to operate even at a high temperature when it is commercialized as a transparent electrode.
5) Flexibility measurement
In this embodiment, the sheet resistance due to bending was measured by bending a doped AGO / Gr / PET sample through a 4-probe measurement using a MSTECH MST5000 Keithley SCS-4200 instrument (Motor controllable motion controller). When bending, the diameter of the bilayer structure of graphene oxide / graphene is 3 mm.
The flexibility of indium tin oxide (ITO / PET), which is most commonly used as a transparent electrode, was confirmed as a comparative group manufactured using a polyethylene terephthalate (PET) 100 μm substrate. In the case of indium tin oxide as a comparative group, resistance was doubled at 5 times of bending cycle, 7.5 times at 50 times, and 46.87 times at 200 times, showing difficulty in using as a transparent transparent electrode. On the other hand, FIG. 7 shows that the double layered structure of the graphene oxide / graphene of the present invention shows almost no change in resistance even when the cycle exceeds 20,000 times. This indicates that it can be applied to a transparent transparent electrode beyond the transparent electrode. The inset of FIG. 7 shows the middle omitted part of the graph of the AGO / Gr / PET sample.
6) Confirm doping characteristics according to carrier type of surface
In this embodiment, the change of sheet resistance and charge neutral point according to the doping effect was measured through a 4-probe measurement using MSTECH MST5000 Keithley SCS-4200 equipment.
The N-doped AGO / Gr / OTS-SiO 2 was immersed in 1.0 mol of sulfuric acid for 24 hours to protonate the amine with ammonium ions. In FIG. 8, it can be confirmed that the P-doping is performed by seeing that the left decode point is shifted to the right. This was immersed in a solution having a pH of 13 for 10 minutes, followed by heat treatment at 120 ° C for 2 hours, and the N-doping characteristics were confirmed by shifting the decarboxylation point to the left again. This confirms that the doping characteristics are different depending on the concentration of the surface carrier of the AGO / Gr structure and it can be used as a sensor by using these characteristics later.
It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics thereof. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.
The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be interpreted as being included in the scope of the present invention .
Claims (12)
Forming a bilayer structure of graphene oxide / graphene by transferring the graphene oxide onto a second graphene; And
Forming a bilayer structure of N-doped graphene oxide / graphene by doping the bilayer structure of the graphene oxide / graphene with an amine-containing functional group
Doping method of graphene,
Wherein the first graphene and the second graphene are formed by a chemical vapor deposition method,
Doping with the amine-containing functional groups can be performed by reacting (3-aminopropyl) triethoxysilane, p-aminophenyltrimethoxysilane, aminotriethoxysilane, N- (2-aminoethyl) (Trimethoxysilylpropyl) diethylenetriamine, N- (trimethoxysilylpropyl) ethylenediaminetriacetic acid, and combinations thereof. In some embodiments, the material is selected from the group consisting of trimethoxysilane, trimethoxysilane, ≪ / RTI >
Wherein the doping is carried out by moving unbound electrons at the amine-containing functional end to the graphene layer through the graphene oxide layer serving as a mediator for movement of the electrons, and
Wherein the bilayer structure of the N-doped graphene oxide / graphene is transparent and flexible,
N-doping method of graphene.
Wherein the first graphene and the second graphene are single-layered.
Treating the bilayer structure of graphene oxide / graphene in a vacuum atmosphere at a temperature ranging from 50 DEG C to 200 DEG C before and after doping with the amine-containing functional group, Lt; / RTI >
Doping said graphene oxide / graphene bilayer structure with said amine-containing functionalities comprises performing in an argon atmosphere.
Doping said graphene oxide / graphene bilayer structure with said amine-containing functional group is carried out by a catalytic reaction.
Doping said graphene oxide / graphene bilayer structure with said amine-containing functional group is carried out in a temperature range of 50 ° C to 100 ° C.
A bilayer structure of N-doped graphene oxide / graphene comprising a bilayer structure of graphene oxide / graphene doped with amine-containing functional groups,
The amine-containing functional groups include (3-aminopropyl) triethoxysilane, p-aminophenyltrimethoxysilane, aminotriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, (3-trimethoxysilylpropyl) diethylenetriamine, N- (trimethoxysilylpropyl) ethylenediamine triacetic acid, and combinations thereof.
Wherein the doping is carried out by moving unbound electrons at the amine-containing functional end to the graphene layer through the graphene oxide layer serving as a mediator for movement of the electrons, and
Wherein the bilayer structure of graphene oxide / graphene is transparent and flexible,
N-doped graphene oxide / graphene bilayer structure.
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