KR101355166B1 - Graphene nano-ribbon, method of fabricating the graphene nano-ribbon, and electronic device using the graphene nano-ribbon - Google Patents

Graphene nano-ribbon, method of fabricating the graphene nano-ribbon, and electronic device using the graphene nano-ribbon Download PDF

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KR101355166B1
KR101355166B1 KR20110115381A KR20110115381A KR101355166B1 KR 101355166 B1 KR101355166 B1 KR 101355166B1 KR 20110115381 A KR20110115381 A KR 20110115381A KR 20110115381 A KR20110115381 A KR 20110115381A KR 101355166 B1 KR101355166 B1 KR 101355166B1
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nanosphere
layer
graphene
ribbon
graphene nano
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KR20130050171A (en
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고건우
심성현
황성원
손철수
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삼성전자주식회사
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Abstract

Disclosed are a method for producing a large-area graphene nano-ribbon by patterning a graphene layer using nanospheres, a graphene nano-ribbon prepared by the above method, and an electronic device using the graphene nano-ribbon. The disclosed method for producing a graphene nano-ribbon comprises the steps of: preparing a nanosphere mold having a plurality of nanospheres arranged in a predetermined pattern; Providing a graphene layer disposed on the substrate; Pressing the nanosphere mold onto the graphene layer such that the plurality of nanospheres are in contact with the graphene layer; And moving the nanosphere mold or graphene layer relative to each other to scrape off the region of the graphene layer in contact with the nanospheres.

Description

Graphene nano-ribbon, method of fabricating the graphene nano-ribbon, and electronic device using the graphene nano-ribbon}

The disclosed embodiments relate to an electronic device using graphene nano-ribbons, graphene nano-ribbons, and graphene nano-ribbons, and more particularly to patterning a graphene layer using nanospheres. It relates to a method for producing a graphene nano-ribbon, a graphene nano-ribbon prepared by the above method, and an electronic device using the graphene nano-ribbon.

Graphene is a two-dimensional thin film of honeycomb structure made of a layer of carbon atoms. The carbon atoms form a carbon hexagonal network surface having a two-dimensional structure upon chemical bonding by sp 2 hybrid orbits. The aggregate of carbon atoms with this planar structure is graphene, which is about 0.34 nm thick, with only one carbon atom. Such graphene is structurally and chemically very stable, and has excellent charge mobility about 100 times faster than silicon, and is capable of flowing about 100 times more current than copper. In addition, graphene has excellent transparency, and may have a higher transparency than indium tin oxide (ITO), which is conventionally used as a transparent electrode. Various studies are being conducted to apply graphene to electronic devices using the above characteristics of graphene.

On the other hand, pure graphene itself, which is not doped or patterned, does not have an energy band gap where the conduction band and the valence band meet each other. In order to utilize graphene in various electronic devices, researches are being conducted on graphene having an energy band gap by doping or patterning the graphene in a specific form. For example, very small patterning of graphene in the form of nano-ribbons is one way to make graphene have an energy band gap. Graphene nano-ribbons can have the same energy band gap as semiconductors by appropriately selecting the size of the width and the shape of the edges.

A method for facilitating the preparation of large area graphene nano-ribbons is provided.

Also provided are graphene nano-ribbons provided by the method, and electronic devices using the graphene nano-ribbons.

According to one type of the present invention, there is provided a method comprising: providing a nanosphere mold having a plurality of nanospheres arranged in a predetermined pattern; Providing a graphene layer disposed on the substrate; Pressing the nanosphere mold onto the graphene layer such that the plurality of nanospheres are in contact with the graphene layer; And moving the nanosphere mold or the substrate relative to each other to scrape the region of the graphene layer in contact with the nanospheres, thereby providing a graphene nano-ribbon.

The preparing of the nanosphere mold may include forming a nanosphere support layer on a mold substrate; Aligning a plurality of nanospheres on the nanosphere support layer; And fixing the plurality of nanospheres to the nanosphere support layer.

In one embodiment, the nanosphere support layer may be made of a thermoplastic resin, in which case the fixing of the plurality of nanospheres to the nanosphere support layer, by heating and softening the nanosphere support layer, the plurality of nanospheres Contacting them with the softened nanosphere support layer seamlessly; And cooling and curing the softened nanosphere support layer.

In another embodiment, the nanosphere support layer may be formed of a thermosetting resin paste, and in this case, fixing the plurality of nanospheres to the nanosphere support layer may include heating and curing the nanosphere support layer.

In another embodiment, the nanosphere support layer may be formed of a photocurable resin paste, and the fixing of the plurality of nanospheres to the nanosphere support layer may include curing by irradiating light on the nanosphere support layer. have.

In an embodiment, the graphene layer may be formed by chemical vapor deposition (CVD) and then transferred onto the substrate.

In another embodiment, the graphene layer may be formed by reducing the graphene oxide applied on the substrate.

According to another type of the present invention, a graphene nano-ribbon formed by the above-described method may be provided.

According to another type of the invention, a substrate; Graphene nano-ribbons disposed on the substrate; A gate insulating layer disposed on the graphene nano-ribbons; A gate disposed on the gate insulating film; And a source and a drain disposed on both sides of the graphene nano-ribbon, for example, and the graphene nano-ribbon may be formed by the above-described method.

Further, according to another type of the invention, the first conductivity type semiconductor layer; An active layer provided on the first conductivity type semiconductor layer and including graphene nano-ribbons; And a second conductive semiconductor layer provided on the active layer, wherein the active layer has a multi-quantum well structure in which a plurality of quantum well layers and a plurality of quantum barrier layers are alternately stacked. The graphene nano-ribbons may be disposed between at least one quantum well layer and at least one quantum barrier layer, and the graphene nano-ribbons may be formed by the above-described method.

In one embodiment, the graphene nano-ribbon on the substrate may be transferred on the surface of the quantum barrier layer or the quantum well layer through heat treatment.

Since the disclosed method for producing graphene nano-ribbons is a method of scraping a graphene layer with a nanosphere mold arranged in a predetermined pattern, a large-area graphene nano-ribbon can be easily manufactured on the surface of the substrate. Therefore, when manufacturing an electronic device using the graphene nano-ribbon, it is advantageous for the integration of the device. In addition, since the manufacturing process of graphene nano-ribbons does not take much time and the nanosphere mold has a long life according to the strength of the nanospheres, one graphene nano-ribbon can continuously produce a large amount of graphene nano-ribbons. have.

In addition, according to the disclosed method, it is possible to easily align the graphene nano-ribbons according to the pattern of the aligned nanospheres can improve the degree of alignment of the graphene nano-ribbon, depending on the direction of movement of the nanosphere mold Patterning of graphene nano-ribbons in the form is possible. In addition, the width of the graphene nano-ribbon can be easily adjusted according to the size and distribution shape of the nanospheres.

In addition, since the disclosed method for producing graphene nano-ribbons is a mechanical method that does not use harmful chemicals or ultraviolet rays, the graphene nano-ribbons have a low possibility of deterioration.

1 is a schematic cross-sectional view illustrating a method of manufacturing a nanosphere mold according to an embodiment.
FIG. 2 is a schematic cross-sectional view illustrating a process of fabricating a graphene nano-ribbon by patterning a graphene layer on a substrate using the nanosphere mold shown in FIG. 1.
3 and 4 are schematic plan views and cross-sectional views of graphene nano-ribbons prepared by the method shown in FIG. 2, respectively.
FIG. 5 is a schematic cross-sectional view of an electronic device using graphene nano-ribbons manufactured by the method illustrated in FIG. 2.
FIG. 6 is a schematic cross-sectional view illustrating another electronic device using graphene nano-ribbons manufactured by the method illustrated in FIG. 2.
FIG. 7 is a schematic cross-sectional view showing an enlarged portion of the active layer shown in FIG. 6.

Hereinafter, with reference to the accompanying drawings, a method for producing a nano-ribbon of a large area by patterning the graphene layer using a nanosphere, a graphene nano-ribbon prepared by the above method, and using the graphene nano-ribbon The electronic device will be described in detail. In the following drawings, like reference numerals refer to like elements, and the size of each element in the drawings may be exaggerated for clarity and convenience of explanation.

1 and 2 are schematic cross-sectional views sequentially showing a method of manufacturing a graphene nano-ribbon according to an embodiment, and FIG. 1 is a schematic cross-sectional view illustrating a method of manufacturing a nanosphere mold for scraping off a graphene layer. FIG. 2 is a schematic cross-sectional view illustrating a process of fabricating a graphene nano-ribbon by patterning a graphene layer on a substrate using the nanosphere mold shown in FIG. 1.

First, referring to FIG. 1A, after forming a nanosphere support layer 12 on a mold substrate 11, a plurality of nanospheres 13 are aligned on the nanosphere support layer 12. do. The nanospheres 13 are spherical nanoparticles having a diameter of about several nm to several hundred nm. Such nanospheres 13 may be made of oxide materials or other metallic materials having relatively good strength, such as, for example, SiO 2 . Currently, many techniques for arranging nanoscale particles in the desired shape have been proposed. For example, a plurality of nanospheres 13 may be arranged in a desired pattern on the nanosphere support layer 12 by a method such as nanosphere lithography. In FIG. 1A, an example in which a plurality of nanospheres 13 are closely spaced on the nanosphere support layer 12 is shown, but this is only one example. The arrangement shape and the diameter of the nanospheres 13 may be appropriately selected depending on the width and shape of the graphene nano-ribbons to be formed later.

In addition, the mold substrate 11 may be made of a material having less thermal or mechanical deformation. For example, silicon, quartz, or a metal material can be used as the material of the mold substrate 11.

In addition, the nanosphere support layer 12 may serve to fix the plurality of nanospheres 13 aligned thereon. The nanosphere support layer 12 may be made of a thermoplastic resin that is softened by heat and then cured by cooling. Then, as shown in (b) of FIG. 1, when the nanosphere support layer 12 is heated, the nanosphere support layer 12 is softened so that a plurality of nanospheres 13 are seamlessly formed with the nanosphere support layer 12. Can be contacted. Thereafter, cooling the nanosphere support layer 12 allows a plurality of nanospheres 13 to be firmly fixed on the nanosphere support layer 12. In addition, a thermosetting resin may be used instead of the thermoplastic resin. For example, when the nanospheres 13 are aligned on the thermosetting resin paste and then heated, the nanospheres 13 to which the nanospheres 13 are fixed may be formed while the thermosetting resin paste is cured. It is also possible to form the nanosphere support layer 12 with a photocurable resin or the like. For example, after aligning the nanospheres 13 on the photocurable resin paste and irradiating light such as UV, the photocurable resin paste is cured to form a nanosphere support layer 12 on which the nanospheres 13 are fixed. It may be. In this manner, the nanosphere mold 10 in which a plurality of nanospheres 13 are fixed in a predetermined pattern may be formed through the process illustrated in FIGS. 1A and 1B.

Meanwhile, referring to FIG. 2, in order to manufacture graphene nano-ribbons, a graphene layer 21 is provided on the substrate 20. Here, the substrate 20 may be made of a material such as, for example, SiO 2 , glass, or polyethylene resin (PET) having excellent bonding with graphene. The graphene layer 21 may be formed on the substrate 20 in various ways. For example, graphene layer 12 may be formed by chemical vapor deposition (CVD) technology and then transferred onto substrate 20. Specifically, after placing a catalyst metal such as nickel (Ni) or copper (Cu) inside the quartz tube, H 2 gas and CH 4 gas are injected into the quartz tube at a temperature of about 1000 ° C. In this case, an inert gas such as argon (Ar) or helium (He) may be injected together. Then, carbon may be crystallized on the surface of the catalyst metal such as nickel or copper to form graphene. Then, when the catalyst metal is immersed in the weakly acidic etching solution, only the graphene remains and the catalyst metal may be removed by the etching solution. After the catalytic metal is completely removed, the graphene layer is placed in a water bath containing DI water to remove the etching solution on the graphene surface. Subsequently, the substrate 20 is placed in a water bath to release the graphene onto the surface of the substrate 20. Then, the graphene layer 21 may be transferred and formed on the substrate 20. Alternatively, the graphene layer 21 may be formed by an oxidation-reduction method. For example, after the graphene oxide layer is formed on the substrate 20, if the graphene oxide layer is reduced with a reducing agent such as hydrazine, the graphene layer 21 may be formed on the substrate 20.

When the graphene layer 21 is provided on the substrate 20 in the above-described manner, as shown in FIG. 2, the nanospheres 13 are in contact with the graphene layer 21 provided on the substrate 20. The nanosphere mold 10 is pressed onto the graphene layer 21. Thereafter, the nanosphere mold 10 or the graphene layer 21 is moved relative to each other to scrape the region of the graphene layer 21 in contact with the nanospheres 13. For example, the substrate 20 in which the nanosphere mold 10 is fixed and the graphene layer 21 may be moved, or the substrate 20 may be fixed and the nanosphere mold 10 may move. Alternatively, both the substrate 20 and the nanosphere mold 10 may move. Depending on the desired pattern of graphene nano-ribbons 22, the relative movement between the substrate 20 and the nanosphere mold 10 may be straight, round or curved. In this process, as the graphene layer 21 is scratched by the nanospheres 13, a part of the graphene layer 21 is separated from the substrate 20.

Then, very narrow graphene nano-ribbons 22 may be formed on the substrate 20. 3 and 4 are schematic plan views and cross-sectional views illustrating exemplary graphene nano-ribbons 22 produced by the method shown in FIG. 2, respectively. 3 illustrates an example in which a plurality of straight band-shaped graphene nano-ribbons 22 are arranged in parallel, but the shape of the graphene nano-ribbons 22 is not limited thereto. For example, various types of graphene nano-ribbons 22 may be formed according to relative movement directions of the nanosphere mold 10 and the graphene 21. In addition, various types of graphene nano-ribbons 22 may be formed according to the size and arrangement of the plurality of nanospheres 13 fixed to the nanosphere mold 10.

Since the graphene nano-ribbon 22 manufacturing method according to the present embodiment described above is a method of scraping the graphene layer 21 with the nanospheres 13 arranged in a predetermined pattern, the graphene nano having a large area Ribbons 22 can be easily fabricated on substrate 20. Therefore, when manufacturing the electronic device using the graphene nano-ribbon 22, it is advantageous for the integration of the device. In addition, since the graphene nano-ribbon 22 does not require many processes, and the life of the nanosphere mold 10 is lengthened according to the strength of the nanospheres 13, one nanosphere mold 10 may be used. A large amount of graphene nano-ribbons 22 can be produced continuously.

In addition, in the above-described embodiment, it is possible to easily align the graphene nano-ribbon 22 according to the alignment pattern of the nanospheres 13, the alignment of the graphene nano-ribbon 22 can be improved According to the movement direction of the nanosphere mold 10, various types of patterning of the graphene nano-ribbons 22 are possible. In addition, the width and the like of the graphene nano-ribbon 22 can be easily adjusted according to the size and distribution shape of the nanospheres 13. Furthermore, the graphene nano-ribbon 22 manufacturing method described above has a low possibility of deterioration of the graphene nano-ribbon 22 because it is a mechanical method that does not use harmful chemicals or ultraviolet rays.

The graphene nano-ribbons 22 thus formed have an energy band gap due to their very narrow width. Thus, graphene nano-ribbons 22 may be used in the manufacture of electronic devices instead of semiconductor materials such as silicon.

5 is a schematic cross-sectional view showing an example of a structure of an electronic device, eg, a thin film transistor, manufactured using the graphene nano-ribbons 22 formed in the above-described manner. Referring to FIG. 5, the gate insulating layer 25 may be formed on the surface of the graphene nano-ribbon 22, and the gate 26 may be sequentially formed on the gate insulating layer 25. The source 23 and the drain 24 may be formed at both sides of the graphene nano-ribbon 22, respectively. Then, the thin film transistor using the graphene nano-ribbons 22 may be completed. The gate insulating layer 25 may be formed of a material such as SiO 2 , SiN x, and the like. The gate 26, the source 23, and the drain 24 may be made of a conductive metal or a conductive metal oxide. Such thin film transistors using graphene nano-ribbons 22 may enable low power and high speed operation due to the excellent electron mobility of graphene.

In addition, the graphene nano-ribbons 22 formed in the above-described manner may be used in semiconductor light emitting devices. For example, FIG. 6 is a schematic cross-sectional view showing the structure of another electronic device, for example, a semiconductor light emitting device, using the graphene nano-ribbon 22. Referring to FIG. 6, the light emitting device 30 is provided on a substrate 31, a first conductive semiconductor layer 32 provided on the substrate 31, and a first conductive semiconductor layer 32. An active layer 33 including the ribbon 22 and a second conductive semiconductor layer 34 provided on the active layer 33 may be included. The first conductivity type semiconductor layer 32 may be, for example, a nitride semiconductor of n-type doped GaN, AlGaN, InGaN, or the like, and the second conductivity type semiconductor layer 34 may be p-type doped GaN, It may be a nitride semiconductor such as AlGaN, InGaN. The active layer 33 may have a multi-quantum well (MQW) structure in which a plurality of GaN-based quantum barrier layers and a plurality of InGaN-based quantum well layers are alternately stacked.

7 is a schematic cross-sectional view showing an enlarged view of the active layer 33. Referring to FIG. 7, the active layer 33 is a multi-quantum well structure in which a quantum barrier layer 33a and a quantum well layer 33b are alternately stacked, and the graphene nano-ribbons 22 have a plurality of quantum barrier layers. It may be provided on at least one layer 33a and the quantum well layer 33b. In the example of FIG. 7, graphene nano-ribbon 22 is disposed between all quantum barrier layers 33a and quantum well layers 33b, but this is only one example. 6 and 7 do not show the pattern of the graphene nano-ribbons 22 for convenience, but the graphene nano-ribbons 22 may be patterned in the form as shown in FIGS. 3 and 4.

The graphene nano-ribbons 22 formed on the substrate 20 in the manner shown in FIG. 2 may be transferred, for example, to the surface of the quantum barrier layer 33a or the quantum well layer 33b. For example, when the graphene nano-ribbon 22 on the substrate 20 is attached to the surface of the quantum barrier layer 33a or the quantum well layer 33b, heat treatment in an oven is performed. The ribbon 22 may be transferred to the quantum barrier layer 33a or the quantum well layer 33b.

The graphene nano-ribbons 22 may improve luminous efficiency by preventing lattice defects of the quantum barrier layer 33a or the quantum well layer 33b, and are emitted from the quantum well layer 33b by the surface plasmon effect. You can also enhance the light.

Until now, a method for producing a large-area nano-ribbon by patterning a graphene layer using nanospheres, graphene nano-ribbons prepared by the above method, and the graphene nano-ribbon Exemplary embodiments of electronic devices used are described and illustrated in the accompanying drawings. It should be understood, however, that such embodiments are merely illustrative of the present invention and not limiting thereof. And it is to be understood that the invention is not limited to the details shown and described. Since various other modifications may occur to those of ordinary skill in the art.

10 ..... Nanosphere Mold 11 ..... Molded Substrate
12 .... Nanosphere Support Layer 13 ..... Nanosphere
20 ..... 21 ..... Graphene layer
22 ..... Graphene Nano-ribbon 23 ..... Source
24 ..... Drain 25 ..... Gate Insulation
26 ..... gate 30 ..... light emitting element
31 ..... substrate 32 ..... first conductive semiconductor layer
33 ..... active layer 34 ..... 2nd conductive semiconductor layer

Claims (11)

Providing a nanosphere mold having a plurality of nanospheres arranged in a predetermined pattern;
Providing a graphene layer disposed on the substrate;
Pressing the nanosphere mold onto the graphene layer such that the plurality of nanospheres are in contact with the graphene layer; And
Moving the nanosphere mold or substrate relative to each other to scrape off the region of the graphene layer in contact with the nanospheres. The method of claim 1,
Preparing the nanosphere mold is:
Forming a nanosphere support layer on the mold substrate;
Aligning a plurality of nanospheres on the nanosphere support layer; And
And fixing the plurality of nanospheres to the nanosphere support layer. 3. The method of claim 2,
The nanosphere support layer is made of a thermoplastic resin,
The fixing of the plurality of nanospheres to the nanosphere support layer is:
Heating and softening the nanosphere support layer, thereby seamlessly contacting the plurality of nanospheres with the softened nanosphere support layer; And
Cooling and curing the softened nanosphere support layer; Graphene nano-ribbon manufacturing method comprising a. 3. The method of claim 2,
The nanosphere support layer is made of a thermosetting resin paste,
The fixing of the plurality of nanospheres to the nanosphere support layer comprises a method for producing a graphene nano-ribbon comprising heating and curing the nanosphere support layer. 3. The method of claim 2,
The nanosphere support layer is made of a photocurable resin paste,
The fixing of the plurality of nanospheres on the nanosphere support layer comprises a method for producing a graphene nano-ribbon comprising curing by irradiating light on the nanosphere support layer. The method of claim 1,
The graphene layer is formed by chemical vapor deposition (CVD) method and the graphene nano-ribbon manufacturing method that is transferred onto the substrate. The method of claim 1,
The graphene layer is a graphene nano-ribbon manufacturing method formed by reducing the graphene oxide applied on the substrate. delete delete A first conductivity type semiconductor layer;
An active layer provided on the first conductivity type semiconductor layer and including graphene nano-ribbons; And
And a second conductivity type semiconductor layer provided on the active layer.
The active layer has a multi-quantum well structure in which a plurality of quantum well layers and a plurality of quantum barrier layers are alternately stacked.
The graphene nano-ribbon is disposed between at least one quantum well layer and at least one quantum barrier layer,
The graphene nano-ribbon is an electronic device formed by the method of any one of claims 1 to 7. 11. The method of claim 10,
The graphene nano-ribbon on the substrate is transferred to the surface of the quantum barrier layer or quantum well layer through a heat treatment.
KR20110115381A 2011-11-07 2011-11-07 Graphene nano-ribbon, method of fabricating the graphene nano-ribbon, and electronic device using the graphene nano-ribbon KR101355166B1 (en)

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KR101428926B1 (en) * 2013-06-03 2014-08-08 고려대학교 산학협력단 Method of transferring a graphene thin layer
KR102018577B1 (en) 2017-12-29 2019-09-05 재단법인 파동에너지 극한제어 연구단 Method of patterning nanomaterial ribbon and nanomaterial ribbon pattern manufactured by the same
KR102140248B1 (en) 2018-12-28 2020-07-31 재단법인 파동에너지 극한제어 연구단 Mehtod of manufacturing meta structure with slot
KR20240091386A (en) 2022-12-13 2024-06-21 재단법인 파동에너지 극한제어 연구단 Nanopatterning method using multiaxial tension

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Adv. Mater. Vol.23, 2011, pages 1246-1251 (2011.01.25.)*

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