KR101475182B1 - Hydrogen surface treated graphene, formation method thereof and electronic device comprising the same - Google Patents

Abstract

The present invention relates to graphene surface-treated with hydrogen, a method of forming the same, and an electronic device including the same. In the graphene according to the present invention, a graphene, which has a band gap and is surface-treated with hydrogen, can be prepared by using a simple method through indirect hydrogen plasma treatment. Also, two regions having different band gaps can be formed through the indirect hydrogen plasma treatment, which can be directly applied to electronic elements such as a transistor and a touch panel to reduce process time and process costs.

Description

[0001] Hydrogen surface treated graphene, a method for forming the same, and an electronic device including the same [0002]

The present invention relates to a graphene surface treated with hydrogen, a method of forming the graphene, and an electronic device including the same.

Graphene is a single flat sheet consisting of sp ² bonds of carbon atoms and can be seen in the form of a hexagonal crystal lattice integrated. Therefore, graphene is a basic structure constituting carbon materials such as graphite, carbon nanotubes, and fullerene in the form of a buckyball. In addition, due to structural differences, carbon atoms appear to be completely different from carbon nanotubes in the form of tubular interconnections. Graphene is emerging as one of the most notable materials in recent years because it has unique physical properties that are visible only in two-dimensional materials, while possessing advantages such as mechanical and electrical properties of carbon nanotubes.

The carbon isotopes mainly formed through covalent bonds are determined by their linear combination of the wave function of the four outermost electrons. Most solids that form a covalent bond have a maximum probability of finding electrons between atoms and atoms. One representative example is diamond, which is one of the carbon isotopes.

In graphene, however, only the linear combination of the three outermost electrons participates in a strong covalent bond between the carbon atoms to form a hexagonal mesh plane, and the wave function of the extra-edge electrons exists in a plane perpendicular to the plane. The state of electrons that participate in strong covalent bonds in parallel with the plane is called σ-orbital, and the state of electrons perpendicular to the plane is called π-orbital. The wavefunctions of electrons near the Fermi level, which determine the physical properties of graphene, consist of a linear combination of π-orbits.

Recently, many research groups have paid attention to the fact that graphene exhibits zero band gap characteristics due to the hexagonal network structure of graphene, the two interstitial triangular sub-lattice structures, and the thickness corresponding to one atom size Respectively. However, due to the zero band gap, graphene has a limited application field such as a metal conductive film or wiring for use as an electronic device.

Currently, research is actively conducted to control the bandgap of graphene. Although studies have been carried out to control the bandgap through the method of making the graphene nanoribbons or nanopatterns and the method of applying the electric field to the substrate, research on the results and methods of precisely controlling the bandgap of the graphene The results have not been released.

Korea Patent Publication No. 2012-0084840

TECHNICAL FIELD The present invention relates to a graphene surface treated with hydrogen, a method of forming the same, and an electronic device including the same, wherein the graphene surface treated with hydrogen is partially subjected to a hydrogen surface treatment, And a second region having a hydrogen adsorption rate of 15 to 25% in the region and the surface.

The present invention can provide a graphene surface treated with hydrogen, a method of forming the graphene, and an electronic device including the same.

As one example of the hydrogen surface-treated graphene,

It is possible to provide a hydrogen-surface-treated graphene having a band gap of 0.1 to 5.5 eV.

For example, the hydrogen-treated graphene may include a first region that is not hydrogen-treated; And a pattern formed of a hydrogen-treated second region.

As one example of the method of forming the hydrogen surface-treated graphene,

And a step of indirectly plasma-treating the surface of the graphene.

For example, the indirect plasma processing may be a surface treatment method using an indirect plasma apparatus and a hydrogen plasma generated by injecting hydrogen gas to generate plasma in the apparatus.

Further, it is possible to provide a method of forming a hydrogen-treated graphene including the pattern, and as one example,

Forming a pattern on the graphene using lithography; And

And subjecting the patterned graphene to indirect-type hydrogen plasma treatment.

As another example of a method of forming a hydrogen-treated graphene including a pattern,

And a step of forming a pattern by irradiating a laser to the hydrogen-surface-treated graphene to form a patterned graphene.

Further, it is possible to provide an electronic device including the graphene subjected to the hydrogen surface treatment.

The graphene according to the present invention can produce a hydrogen-surface-treated graphene having a band gap by a simple method through indirect hydrogen plasma treatment. In addition, the indirect hydrogen plasma treatment can form two regions having different band gaps, which can be directly applied to electronic devices such as transistors and touch panels, thereby reducing processing time and process cost.

1 is a schematic diagram of a method for forming graphene in one embodiment.
2 is a schematic view showing the appearance of an electronic apparatus in one embodiment.
3 is a schematic diagram showing a touch panel in one embodiment.
FIG. 4 is a graph showing the band gap change of graphene according to the hydrogen plasma surface treatment time in one embodiment. FIG.
Figure 5 is a Raman spectrum along the region of graphene in one embodiment.
6 is a graph showing a hydrogen coverage rate according to a hydrogen plasma surface treatment time of a graphene surface in one embodiment.
FIG. 7 shows, in one embodiment, (a) Raman spectrum and (b) I _D / I _{D 'as} a function of hydrogen plasma surface treatment time. .
FIG. 8 is a graph showing a change in band gap of a hydrogen-treated graphene according to a heat treatment time in an embodiment. FIG.

The present invention can provide a graphene surface treated with hydrogen and a method of forming the graphene and an electronic device including the same.

As one example of the hydrogen surface-treated graphene,

It is possible to provide a hydrogen-surface-treated graphene having a band gap of 0.1 to 5.5 eV.

For example, the hydrogen surface treatment can be performed by hydrogen plasma treatment, wherein an indirect plasma apparatus can be used.

Ungreased graphene forms a two-dimensional hexagonal net shape through a strong covalent bond between carbon atoms. The graphene has a strong covalent bond between the carbon atoms forming the plane, which is a sp ² bond structure, contains a sigma-bond, has an sp ³ bond structure perpendicular to the plane, one electron remains in the p- bond. At this time, it is possible to exhibit a high conductivity characteristic through a π-bond which is not vertically bonded to the plane of graphene. However, in the present invention, graphene adsorbs hydrogen to an electron site formed in a p-orbital that is not vertically bonded to the plane of the graphene, so that it can block the? Bond and impart a band gap. Therefore, the present invention can control the conductivity characteristic of graphene by controlling the degree of hydrogen adsorption.

For example, the bandgap may be 0.1 to 0.5 eV, 1.0 to 5.5 eV, or 1.5 to 3.5 eV. And can be used as various electronic materials through a band gap within the above range. Specifically, conventional graphene has high mechanical and electrical properties, but has limited use as an electronic material requiring a band gap due to a zero band gap. However, the graphene according to the present invention can overcome the above-mentioned problem through hydrogen surface treatment.

Wherein the hydrogen-treated graphene has a first region that is not hydrogen-surface-treated; And

And a pattern formed by the hydrogen-treated second region.

Specifically, as described above, a pattern having different band gaps in each region can be formed through hydrogen treatment.

For example, the first region may have a band gap of 0.1 to 0.5 eV,

And the second region may have a band gap of 1.0 to 5.5 eV.

Specifically, the first region of graphene having a low hydrogen adsorption ratio on the surface can exhibit high conductivity characteristics as described above. Further, the second region of the hydrogen-treated graphene adsorbs hydrogen to the electron site formed in the p-orbital not perpendicular to the plane of the graphene according to the hydrogen adsorption rate of the surface, Thereby controlling the conductivity characteristics of graphene by adjusting the bandgap.

The bandgap of the first region may be, for example, 0.1 to 0.5 eV, 0.1 to 0.4 eV, or 0.1 to 0.3 eV. The first region having a band gap within the above range may mean a semi-conductive region. Further, the bandgap of the second region may be 1.0 to 5.0 eV, 2.5 to 5.0 eV, or 3.5 to 5.0 eV, for example. The second region having a bandgap within the above range may mean a semi-conductive or non-conductive region.

In one embodiment, the sheet resistance of the first region is 500 to 1000 OMEGA / sq,

The sheet resistance of the second region may be between 1 and 500 MΩ / sq.

For example, the sheet resistance of the first region may be 500 to 900 Ω / sq, 500 to 800 Ω / sq or 500 to 600 Ω / sq, and the sheet resistance of the second region may be 1 to 450 MΩ / To 400 M OMEGA / sq or from 100 to 300 M OMEGA / sq. By controlling the sheet resistance of each region to the above range, patterned graphene having different conductivity characteristics can be produced.

The graphene having two regions having different band gaps according to the present invention can be realized by a simple indirect hydrogen plasma process or a laser irradiation of indirect hydrogen plasma treated graphene.

The graphene may satisfy the following equation (1).

[Equation 1]

? E ^* ? 1.5

In the above equation (1)

? E ^* denotes the chrominance of the first region and the second region measured using the CIE (Commosition international de l'eclairage) color coordinate system.

Specifically, the ΔE ^* value was used in the CIE Lab color space, which is a color value defined by CIE (Commossion international del'Eclairage). The CIE Lab color space is a globally standardized color space because it can almost match the color difference that can be detected by our eyes and the numerical value in the color space. The color difference in the CIE Lab space is the distance between positions in the coordinates. If the distances are different from each other in three dimensions, the color difference is large. Such a color difference is represented by? E ^* in a digital representation. Usually, if ΔE ^* is less than 0.5, the color difference is hardly felt. If the difference is less than 1.5, the color difference is extremely small. However, when the value of DELTA E ^* exceeds 1.5, the color difference can be felt. When the value of DELTA E ^* is 2.0 or more, the color difference becomes extreme. However, this is commonly used, but there is no particular standard in common, which may mean, for example, that when the product is produced, the color difference management for the product is being maintained if the ΔE ^* value is maintained at 0.8 to 1.5.

The DELTA E ^* value can be calculated through the following equation (3).

&Quot; (3) "

In Equation (3),? L ^* means the difference in brightness between the components L1 ^* and L2 ^* of the color coordinates E1 and E2 of the two colors. Also, Δa ^* also E1 and E2 of the component a1 ^* and a2 ^* in the car in red-yellow-green (Red-Green) drive of the mean difference in color, and Δb ^* also E1 and E2 of the component b1 ^* and b2 ^* - means a car of blue (Yellow-Blue) color.

Specifically, in Equation (1), the DELTA E ^* value can control the chrominance of the first region and the second region of the graphene according to the present invention to be below the level at which the observer perceives the chrominance. Accordingly, it is possible to solve the problem that a pattern generated in an electronic device manufactured through conventional processes such as etching and etching is recognized by an observer. For example, the? E ^* value may be 0.001 to 1.5, 0.001 to 1.2, 0.001 to 1.0, or 0.001 to 0.8.

The hydrogen adsorption ratio of the surface of the first region is 5 to 13%

The hydrogen adsorption rate of the surface of the second region may be between 15 and 25%.

The hydrogen adsorption rate of the surface means the ratio of hydrogen adsorbed on the graphene surface with the maximum value of the range in which hydrogen can be adhered on the graphene surface set at 100%.

Specifically, the first region is either not directly exposed to the indirect hydrogen plasma treatment, or is a partially reduced region through the laser, the hydrogen adsorption rate of the surface may appear as 5 to 13% and in some cases as less than 5% You can fly. For example, the hydrogen adsorption rate of the surface of the first region may be from 5 to 12%, from 5 to 10%, or from 5 to 8%. The first region has a hydrogen adsorption rate within the above range, exhibits a low band gap and a low sheet resistance, and can form an inverse conductive region.

Further, the second region is a region subjected to hydrogen surface treatment, and can exhibit a hydrogen adsorption ratio higher than that of the first region. For example, the hydrogen adsorption rate of the surface of the second region may be from 17 to 25%, from 20 to 25%, or from 22 to 25%. The second region exhibits a band gap of 2.0 to 5.5 eV by exhibiting a hydrogen adsorption rate within the above range, exhibits a high sheet resistance, and can form a semi-conductive region or a nonconductive region.

The hole mobility in the first region is 100 to 500 cm ² / V · s,

The hole mobility in the second region may be between 1 and 80 cm ² / V · s.

For example, graphene has high mobility properties such as electrical conductivity and carrier mobility. However, by applying a hydrogen surface treatment to the graphene, the band gap can be given to lower the mobility. For example, when the graphene is subjected to a hydrogen surface treatment for about 5 seconds, the band gap is about 1 to 2 eV, and the hole mobility of graphene is 10 to 80 cm ² / V · s Can be lowered. In addition, when the graphene is subjected to the hydrogen surface treatment for about 10 seconds or more, the band gap is about 3 to 5.5 eV, and the hole mobility of the graphene is lowered to 1 to 5 cm ² / V · s have. The hole mobility within the above range is equivalent to or better than the hole mobility of silicon (Si) widely used as an electronic device such as a semiconductor due to its high mobility characteristic compared to conventional ones, And hole mobility.

The graphene subjected to the hydrogen surface treatment can satisfy the following equation (2).

&Quot; (2) "

13? I _D / I _{D '} ≤ 20

In Equation (2)

I _D is the intensity of the peak near Raman shift 1350 cm ^-1 ,

I _{D '} is the intensity of the peak near Raman shift 1620 cm ^-1 .

Specifically, this can be confirmed by measuring the Raman spectrum of graphene according to the present invention. I _D is the intensity of the D peak in the vicinity of Raman shift 1350 cm ^-1 , which may be a peak indicating that hydrogen is adsorbed on the graphene. For example, the vicinity of 1350 cm ^-1 is 1300 to 1400 cm ^- may refer to ^one. Further, I _{D '} is a D' peak represented by Raman shift near 1620 cm ^-1 , which may be a peak indicating a defect that can be exhibited in the process of hydrogen adsorption on graphene. For example, the vicinity of 1620 cm ^-1 is 1600 to 1650 cm ^- may refer to ^one. At this time, as the defect, an atomic vacancy type defect and an sp ³ type defect may exist. Among these, defects of the atomic cavity type are permanent damage defects. In order to obtain graphene with a less defective hydrogen surface, a reversible sp ³ type defect may be preferred.

The type of defect can be deduced through the above I _D / I _{D '} . For example, if I _D / I _{D '} is greater than 13, it can mean a sp ³ type defect.

Further, the graphene subjected to the hydrogen surface treatment can satisfy the following equation (3).

3 ≤ I _D / I _G ≤ 5

In Equation (3)

I _D is the intensity of the peak near Raman shift 1350 cm ^-1 ,

I _G is the intensity of the peak at around Raman shift 1600 cm ^-1 .

Specifically, this can be confirmed by measuring the Raman spectrum of graphene according to the present invention. At this time, I _D is the intensity of the D peak shown near Raman shift 1350 cm ^-1 as described above, and may be a peak indicating that hydrogen is adsorbed on the graphene. In addition, I _G is the intensity of the G peak showing near the Raman shift 1600 cm ^-1, for example, the vicinity of 1600 cm ^-1 is 1580 to 1610 cm ^- may refer to ^one. For example, I _D / I _G may be from 3 to 4.5, from 3 to 4, or from 4 to 5. Through the I _D / I _G in the above range, hydrogen is adsorbed on the surface of graphene to confirm that a band gap is formed.

As one of the methods for confirming that the generation of defects of the atomic cavity type that gives permanent damage is small, there is a method of reducing the graphene in the hydrogen surface treated region to graphene which has not been subjected to hydrogen surface treatment through a heat treatment process or a laser irradiation process Method. Specifically, indirect hydrogen plasma treatment may be performed on the second region of graphene to hydrogenate the graphene surface. Then, it can be reduced to graphene before the plasma treatment by heat treatment at a temperature of 150 ° C or higher for 40 minutes to 300 minutes. Traditionally, in the process of hydrogen surface treatment of graphene surfaces, graphene can cause defects, which can accompany defects that cause permanent damage. However, the hydrogen-treated graphene according to the present invention can be completely desorbed and returned to the conventional hydrogen-untreated graphene by heat treatment. This may mean that the graphenes are surface-treated and no defects have occurred during the reduction to graphene before the surface treatment. The method of confirming the reduction of the graphene can be confirmed by measuring the band gap. For example, graphene with a bandgap of about 5 eV through a hydrogen surface treatment can be closed to a band gap of less than 0.1 eV upon heat treatment at a temperature of 150 ° C or higher for about 40 minutes, and a substantially heat- The gap is 0 eV and can be reduced to the original graphene without defects.

The graphene may be a laminated structure of 2 to 20 layers.

As one example, n (n is an arbitrary integer between 2 and 20) th layers of the stacked graphene may be formed such that a pattern including a first region that is not hydrogen-treated and a second region that is hydrogen- .

Specifically, graphene may be formed in 2 to 20 layers as required, and at least one of the layers may be patterned to include a first region not subjected to hydrogen surface treatment and a second region subjected to hydrogen surface treatment . As a result, graphenes having two regions having different band gaps on the same surface can be formed.

Optionally, each of the layers comprises a first region that is not hydrogen-treated and a second region that is hydrogen-treated,

The n (n is an arbitrary integer between 2 and 20) th layer and the (n-1) th layer of the stacked graphene may be formed in different patterns of the hydrogen surface-treated regions.

The pattern of each layer can be formed variously according to need by a method of performing hydrogen plasma treatment on the patterned graphene using the lithography or a method of laser treating the patterned graphene with hydrogen plasma treatment.

Further, the present invention can provide a method for surface treatment of graphene. As an example,

And indirectly plasma-treating the surface of the graphene. Specifically, the indirect plasma process is different from the direct plasma process for graphene, and the plasma is generated indirectly by exposing the plasma to the graphene, so that the plasma does not come into direct contact with the graphene, It is possible to surface the graphene without surface defects of the graphene.

For example, in the indirect plasma processing step, after the gas is injected into the indirect plasma apparatus, the generated plasma can be processed, and at this time, plasma generation can be precisely controlled using a controller .

In the indirect plasma processing step,

Hydrogen gas can be used to generate the plasma. For example, the gas injected into the indirect plasma apparatus may be a hydrogen gas, and the surface of the graphene can be hydrogen-treated using the hydrogen plasma generated through the hydrogen plasma. Conventionally, hydrogen and argon mixed gas have been used in the plasma generation process. However, this has a disadvantage in that defects can be generated on the surface of graphene due to residual argon in the surface treatment of graphene. However, in the present invention, hydrogen gas is used, and when the surface of the graphene is treated by using the generated hydrogen plasma, defects on the surface of the hydrogen-treated graphene can be prevented.

The internal partial pressure of the hydrogen gas injected into the plasma apparatus may be 15 mtorr or less. For example, the internal partial pressure of the hydrogen gas may be 1 to 15 mtorr, 5 to 15 mtorr, or 10 to 15 mtorr. By adjusting the internal partial pressure of the hydrogen gas within the above range, the flow rate of the hydrogen gas can be controlled, and the amount and energy of the hydrogen plasma can be controlled within a range that does not cause defects in the graphene surface treatment process.

The graphene may be disposed at an angle of 0 to 90 degrees with respect to the plasma processing direction. For example, a hydrogen plasma generated in an indirect plasma apparatus flows through an in-apparatus flow path, and a graphene sample can be positioned at an angle of 0 to 90 degrees with respect to the hydrogen plasma flow to produce a hydrogen- have. For example, the position angle of the graphene can be positioned at an angle of 0 to 5 degrees, 5 to 90 degrees, or 60 to 90 degrees. In this case, the 0 ° may mean horizontally, and 90 ° may mean vertically. By controlling the angle within the above range, the degree of hydrogen surface treatment of graphene can be controlled.

The plasma treatment may be performed for 1 to 1000 seconds. For example, depending on the treatment time, the amount of hydrogen adsorbed on the graphene surface can be controlled, and when subjected to plasma treatment for 100 seconds or more, the hydrogen surface-treated surface area of graphene can be about 25%.

As described above, the hydrogen-treated graphene produced by the above method adsorbs hydrogen to the electron sites formed in the p-orbital that is not vertically bonded to the plane of graphene, thereby blocking the π-bond and imparting a bandgap can do. At this time, the π-bonds to be interrupted are not permanently damaged but can be reduced to graphene before the plasma treatment through heat treatment. The heat treatment can be carried out at a temperature of 150 ° C or higher, whereby the hydrogen can be desorbed. As a result, it can be confirmed that when the graphene is subjected to a hydrogen surface treatment by the method according to the present invention, it is not accompanied by a defect causing permanent damage.

In addition, the present invention can provide a method of forming graphene including a pattern. As an example,

Forming a pattern on the graphene using lithography; And

And a step of hydrogen plasma treatment of the patterned graphene.

For example, the graphene may be formed on a substrate. Glass, sapphire, PC (polycarbonate), PI (polyimide), PET (polyethylene terephthalate), PES (polyethylene terephthalate), and the like. (polyethersulfone), and PMMA (polymethymethacrylate).

Then, a pattern can be formed on the graphene using lithography, and the shape of the pattern is not particularly limited, and can be variously manufactured according to the application field. The pattern thus formed may result in areas where the graphene is exposed and areas that are not exposed. On the other hand, when the hydrogen plasma treatment is performed, the exposed portion may be subjected to a hydrogen surface treatment to form a constant bandgap.

The band gap of the region where the pattern is formed and is not exposed to the hydrogen plasma is 0.1 to 0.5 eV,

The bandgap of the region exposed to the hydrogen plasma without forming a pattern may be 1.0 to 5.5 eV.

For example, a portion that is not directly hydrogen-treated due to a pattern formed using lithography may have a band gap of 0.1 to 0.5 eV, and a hydrogen-treated portion may have a band gap of 1.0 to 5.5 eV .

In this manner, graphene having two regions having different band gaps can be manufactured. This is because, compared with electronic devices such as transistors, which have been formed through a plurality of conventional etching and etching processes, .

The hydrogen plasma treatment may be an indirect plasma treatment as described above.

The plasma treatment may be performed for 1 to 1000 seconds. As a result, the bandgap of the first region where the pattern is formed and not directly surface-treated can be represented by 0.1 to 0.5 eV, and the bandgap of the second region exposed to the hydrogen plasma without patterning is 1.0 to 5.5 eV .

As another example of the method for forming graphene including the pattern,

And a step of forming a pattern by irradiating a laser to the hydrogen-surface-treated graphene to form a patterned graphene.

For example, graphene subjected to hydrogen surface treatment through an indirect type plasma treatment can be formed by hydrogen plasma treatment of the graphene surface by a hydrogen plasma treatment method equivalent to that described above. Specifically, the hydrogen-treated graphene is irradiated with a laser to reduce the hydrogen-surface-treated graphene in a desired region, and can be reduced to a structure re-organized into a plane hexagonal structure unique to graphene before the plasma treatment. In this case, the region reduced to the graphene before the plasma treatment through laser irradiation may be the first region, and the region other than the region may be the second region, through which the patterned graphene can be formed .

For example, the laser irradiation may be performed by sequential lateral solid-crystallization (SLS), excimer laser annealing (ELA), furnace annealing (FA), or rapid thermal annealing rapid thermal annealing (RTA). Specifically, the laser irradiation can be performed by an excimer laser crystallization method, which allows heat treatment at a low temperature, so that the graphene surface can be reduced in a short time while minimizing defects on the graphene surface.

The band gap of the pattern region formed by irradiating the laser is 0.1 to 0.5 eV,

The band gap of the region not irradiated with the laser may be 1.0 to 5.5 eV.

Specifically, the bandgap of the pattern formed by reduction of the hydrogen-treated graphene by heat treatment using laser irradiation is 0.1 to 0.5 eV, and the band gap of the hydrogen-treated graphene without laser irradiation is 1.0 to 5.5 eV Lt; / RTI >

The temperature of the graphene surface irradiated with the laser may be 200 ° C or higher. Specifically, the temperature of the graphene surface irradiated with the laser may be 200 to 300 ° C, 220 to 300 ° C, or 250 to 280 ° C. By controlling the temperature of the surface of the graphene irradiated with the laser within the above range, the graphene surface can be reduced by heat treatment for a short time while minimizing defects on the graphene surface. As a result, patterned graphene can be produced using a laser on hydrogenated graphene.

The present invention can provide an electronic device comprising the hydrogen-treated graphene. For example, the electronic device may include a transistor and a touch panel.

The transistor can be applied as an electronic component including an electronic element, a memory element, and a resistor.

For example, a method of fabricating the transistor is shown in FIG. Referring to FIG. 1, after a photosensitive material is coated on a graphene 10, a pattern of a photosensitive material 20 having a pattern similar to that of a mask is formed through exposure and development using a mask formed by lithography. Thereafter, the graphene having the pattern of the photosensitive material 20 is subjected to a hydrogen plasma treatment and the pattern of the photosensitive material 20 is removed. The pattern of the photosensitive material 20 acts as a protective film for the hydrogen plasma to form graphene having the graphene region 12 in which defects are not generated. Then, a metal pad (not shown) for removing the pattern of the photosensitive material and providing an electrical connecting terminal to the outside of the graphene may be formed to form a precise wiring on a single graphene. At this time, the graphene region having the electrical characteristic changed corresponds to the second region of the graphene according to the present invention, and the graphene region having no defect may correspond to the first region of the graphene according to the present invention. In addition, the pattern is not limited thereto, and may be changed depending on the use. The degree of change of the electrical characteristic can be changed flexibly according to the application, and it can be controlled by varying the plasma intensity and the processing angle. According to the present invention, the graphene region 11 in which the electrical characteristics are changed and the graphene region 12 in which no defect is generated can exhibit a color difference low enough that the viewer can not recognize.

In addition, the touch pad is a device for detecting a change in capacitance of a touch pad corresponding to a position where a touch is performed, and may be formed in a patterned structure having two different areas of sheet resistance. In this case, when a touch is performed on the touch pad, an electrical signal generated in a region corresponding to the touch-performed position is transmitted to the control unit through the corresponding region and the wiring, and coordinates corresponding to the touch- It can be recognized. In this case, the touch pad proposed in the present invention can be applied as a component of a touch panel.

Also, the touch panel may be applied to an electronic apparatus to which a touch sensing apparatus can be applied. Specifically, a cathode ray tube (CRT), a liquid crystal display (LCD), a field emission display (FED), a plasma display panel (PDP) And a liquid crystal display (LCD), which is provided on a display surface of an image display device such as an electro luminescence device (ELD), and which presses (presses or touches) the touch panel while the user views the image display device, It is kind. 2, the portable telephone 100 includes a display device 110 for outputting a screen, an input unit 120, an audio unit 130 for outputting audio, and the like. The display device 110 And a touch panel as a touch sensing device.

The structure of the touch panel is shown in FIG. 3, the touch panel 200 includes a substrate 210 and a plurality of sensing electrodes 220 and 230 provided on the substrate 210. The plurality of sensing electrodes 220 and 230 may include a first electrode 220 for sensing the Y-axis position of the touch input and a second electrode 230 for sensing the X- have. In FIG. 3, eight first and second electrodes 220 and 230 are provided. Each of the first and second electrodes 220 and 230 includes sensing channels X1 to Xn, It is connected to X8 and Y1 to Y8. 3, the first electrode 220 and the second electrode 230 are formed on the same surface of the substrate 210. However, the first electrode 220 and the second electrode 230 may be separately formed on the upper and lower surfaces of the substrate 210, And may be formed on the transparent substrate 210, respectively. That is, the plan view shown in FIG. 3 corresponds to only one embodiment for explaining the touch panel according to the present invention.

3, a touch panel according to the present invention includes a graphene layer formed on a substrate, a photosensitive material coated on the graphene layer, and exposure and development using a mask formed using lithography A pattern of a rhombic or diamond-shaped photosensitive material as shown in Fig. 3 was prepared. Then, the graphene layer having the photosensitive material pattern is subjected to hydrogen plasma treatment. When the photosensitive material pattern is removed, a graphene region (second region) having a partial hydrogen plasma treatment according to the pattern and having an electrical characteristic changed, The pattern of the material acts as a protective film for the hydrogen plasma to form graphene having a graphene region (first region) in which defects are not generated. For example, in the structure of FIG. 3, the first electrode may denote a first region of graphene according to the present invention, and the second electrode may denote a second region of graphene according to the present invention. The touch panel In addition, the graphene region 11 in which the electrical characteristics are changed and the graphene region 12 in which no defect is generated can exhibit a color difference as low as the viewer can not recognize.

Hereinafter, the present invention will be described in more detail with reference to the following Examples. However, the scope of the present invention is not limited by the following Examples.

Example  1: Hydrogen treated surface Grapina  Produce

The injection amount of hydrogen gas was finely controlled using an MFC (mass flow controller) installed in the indirect type plasma device and then injected into the device. The partial pressure of gas in the apparatus under vacuum was then maintained at 15 mtorr or less, the voltage was supplied, and the hydrogen plasma was generated. The generated hydrogen plasma flows along the flow path in the apparatus, and the graphene sample is placed on the flow, and the graphene is subjected to hydrogen surface treatment for 1 to 300 seconds.

Then, the band gap of the produced hydrogen-surface-treated graphene was measured. The results are shown in Fig. Referring to FIG. 4, when the hydrogen treatment time is varied from 1 to 200 seconds, the band gap to be controlled can be confirmed. As a result, it was confirmed that a band gap of about 4.7 eV was formed.

Example  2: patterned Grapina  Produce

After the graphenes were coated on the substrate, a photosensitive material was applied, a mask having a pattern was formed, and exposed and developed. The mask, photosensitive material, exposure and development were performed using lithography used in conventional semiconductor processing, and the exposure used light containing 13 nm (EUV) to 435 nm (g-line).

Then, the graphene region from which the photosensitive material was removed by the development was subjected to hydrogen plasma treatment. The plasma treatment was performed by finely controlling the injection amount of hydrogen gas using an MFC (mass flow controller) installed in an indirect type plasma apparatus, and injecting it into the apparatus. Specifically, the internal partial pressure of gas in the vacuum apparatus was maintained at 15 mtorr or less, the voltage was supplied, and the hydrogen plasma was generated. The generated hydrogen plasma flows along the flow path in the apparatus, placing the graphene sample on the flow, and hydrogenating the graphene for about 700 seconds.

Raman spectra were measured on the partially hydrotreated graphene prepared above. The results are shown in Fig. 5A, the surface of the first region PG and the pattern of the second region HG are formed through a graphene etching (Ar + ion etching) and a hydrogenation (hydrogenation) Results. In addition, b shows a Raman spectrum of a region (first region) where a mask having a pattern is formed and a region (second region) where a mask having a pattern is not formed. Specifically, in the case of the first region PG, it was confirmed that a strong peak was ^{observed in the} vicinity of Raman shift of 2600 to 2700 cm ^-1 . Further, in the case of the second region, it was confirmed that a strong peak was shown in the vicinity of Raman shift 1300 to 1400 cm ^-1 .

Example  3: Patterned Grapina  Produce

The surface of the graphene was subjected to hydrogen plasma treatment. The plasma treatment was performed by finely controlling the injection amount of hydrogen gas using an MFC (mass flow controller) installed in an indirect type plasma apparatus, and injecting it into the apparatus. Specifically, the internal partial pressure of gas in the vacuum apparatus was maintained at 15 mtorr or less, the voltage was supplied, and the hydrogen plasma was generated. The generated hydrogen plasma flows along the flow path in the apparatus, placing the graphene sample on the flow, and hydrogenating the graphene for about 700 seconds.

Then, a specific region was reduced on the hydrogen-treated graphene by heat treatment using excimer laser annealing (ELA) to form a pattern on the graphene. At this time, the temperature of the surface of the graphene irradiated with the laser was adjusted to 200 to 300 캜.

Experimental Example  One

In Example 2, the hydrogen surface treatment time was varied from 1 to 200 seconds. Then, the hydrogen coverage of the graphene surface was measured for the first region and the second region. This is shown in Fig. Referring to FIG. 6, the hydrogen coverage of the first region can be represented by the region where the hydrogen coverage is 13% or less. On the other hand, as the hydrogen surface treatment time increases, a region where the hydrogen coverage ratio is 15 to 25% can represent the hydrogen coverage of the second region surface. Specifically, when the hydrogen plasma treatment is performed for 30 seconds or more, a high hydrogen coverage rate of 20% or more can be confirmed.

Further, the band gap was measured for the second region, and it was confirmed that as the plasma treatment time was increased, the band gap increased to a maximum of 5.5 eV.

As a result, it was found that the hydrogen surface-treated surface area of graphene was increased as the hydrogen surface treatment time of graphene was increased, and thus the band gap could be imparted to the graphene. In addition, it has been confirmed that, in the case of using a patterned mask, two regions having different band gaps can be formed on the graphene by a simple method through the hydrogen surface treatment.

Experimental Example  2

In the first embodiment, band gap measurement experiments were performed by varying the injection flow rate of hydrogen and the positional angle of the graphene sample with respect to the hydrogen plasma flow. As a result, it was confirmed that when the flow rate of hydrogen is the same, the bandgap increases as the position angle of the graphene sample increases. Also, it was confirmed that the bandgap increases as the injection flow rate of hydrogen increases when the positional angle of the graphene sample is the same.

Experimental Example  3

In Experimental Example 1, the Raman spectrum of the hydrogen-surface-treated graphene produced by varying the treatment time from 1 to 200 seconds was measured. This is shown in Fig. 7A. Further, in the Raman spectrum, the D 'peak intensity (the intensity of the peak at around 1620 cm ^-1 , I _D' (I _D / I _{D '} ) relative to the ratio D of the peak intensity (intensity of the peak at around 1350 cm ^-1 , I _D ) ratio was measured and shown in Fig. 7 (b). 7B, I _D / I _{D '} Value of 13 or more. Through this, it can be seen that the hydrogen surface of graphene, the original graphene reducible sp ³ types of defects in the non-defect atomic type defects in the cavity (atomic vacancy) to permanent damage to processing occurs in accordance with the present invention there was.

Experimental Example  4

The hole mobility of the hydrogen-treated second region was measured by changing the treatment time of the hydrogen-treated graphene produced by the method according to Example 2 to 1 to 200 seconds. As a result, it was confirmed that as the plasma treatment time increases, the sheet resistance of the second region increases and the hole mobility decreases. As a result, it was confirmed that a band gap was formed in the second region. In addition, it can be confirmed that when the hydrogen plasma treatment is performed on the graphene for about 5 seconds, the hole mobility of silicon (Si), which is widely used as a conventional electronic material, is 160 cm ² / V · s or more.

Experimental Example  5

Experiments were conducted in which the hydrogen-treated graphene prepared by the method according to Example 1 was subjected to heat treatment and reduced to graphene before the hydrogen surface treatment. At this time, the heat treatment was performed at 180 DEG C for 1 to 120 minutes, which is shown in FIG. 8, the band gap of the hydrogen-treated graphene of Example 1, which had a band gap of 4.7 eV, decreased as the annealing time was increased. When the annealing was performed for about 40 seconds or more, the band gap was 0 eV, It was confirmed that graphene before the hydrogen surface treatment was reduced without defects.

10: Grain Fins
11: Graphene region with changed electrical properties
12: Graphene area without defect
20: Photosensitive material
100: Portable telephone
110: display device
120: Input unit
130: Audio part
200: touch panel
210: substrate
220: first electrode
230: second electrode

Claims (22)

A band gap of 0.1 to 5.5 eV,
A first region not subjected to hydrogen surface treatment; And
A hydrogen-surface treated graphene comprising a pattern formed into a second hydrogen-treated region.
delete The method according to claim 1,
The first region has a band gap of 0.1 to 0.5 eV,
And the second region has a band gap of 1.0 to 5.5 eV.
The method according to claim 1,
The sheet resistance of the first region is 500 to 1000 Ω / sq,
And the sheet resistance of the second region is 1 to 500 M OMEGA / sq.
The method of claim 1, wherein
Wherein graphene satisfies the following formula:
[Equation 1]
? E ^* ? 1.5
In the above equation (1)
? E ^* denotes the chrominance of the first region and the second region measured using the CIE (Commosition international de l'eclairage) color coordinate system.
The method according to claim 1,
The hydrogen adsorption rate of the surface of the first region is 5 to 13%
And the hydrogen adsorption rate of the surface of the second region is 15 to 25%.
The method according to claim 1,
The hole mobility in the first region is 100 to 500 cm ² / V · s,
And the second region has a hole mobility of 1 to 80 cm ² / V · s.
The method according to claim 1,
A hydrogen-treated graphene characterized by satisfying the following formula (2):
&Quot; (2) "
13? I _D / I _{D '} ≤ 20
In Equation (2)
I _D is the intensity of the peak near Raman shift 1350 cm ^-1 ,
I _{D '} Lt; ^-1 > cm < ^{-1 &} gt ;.
The method according to claim 1,
A hydrogen-treated graphene characterized by satisfying the following formula (3):
&Quot; (3) "
3 ≤ I _D / I _G ≤ 5
In Equation (3)
I _D is the intensity of the peak near Raman shift 1350 cm ^-1 ,
I _G is the intensity of the peak at around Raman shift 1600 cm ^-1 .
The method according to claim 1,
Wherein the graphene is reduced to graphene which has not been subjected to hydrogen surface treatment when the graphene is subjected to heat treatment at a temperature of 150 DEG C or more.
The method according to claim 1,
The graphene is a layered structure of 2 to 20 layers,
Wherein n (n is an arbitrary integer of 2 to 20) layers of the laminated graphene has a pattern including a first region that is not subjected to a hydrogen surface treatment and a second region that is subjected to a hydrogen surface treatment. Graphene.
The method according to claim 1,
The graphene is a layered structure of 2 to 20 layers,
Each layer comprising a first region that is not hydrogen-treated and a second region that is hydrogen-treated,
Wherein n (n is an arbitrary integer between 2 and 20) th layer and n-1 th layer of the laminated graphene have different patterns of hydrogen surface-treated regions.
delete delete delete Forming a pattern on the graphene using lithography; And
And subjecting the patterned graphene to hydrogen plasma treatment.
17. The method of claim 16,
The band gap of the region where the pattern is formed and is not exposed to the hydrogen plasma is 0.1 to 0.5 eV,
Wherein the bandgap of the region where the pattern is not formed and is exposed to the hydrogen plasma is 1.0 to 5.5 eV.
And irradiating the hydrogen-surface-treated graphene with a laser to form a pattern.
19. The method of claim 18,
The band gap of the pattern region formed by irradiating the laser is 0.1 to 0.5 eV,
Wherein the bandgap of the region not irradiated with the laser is 1.0 to 5.5 eV.
19. The method of claim 18,
Wherein the temperature of the graphene surface to which the laser is irradiated is 200 DEG C or more.
An electronic device comprising the hydrogen-treated graphene according to claim 1.
22. The method of claim 21,
A transistor, and a touch panel.

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