KR101754783B1 - Transfering method of nanorod - Google Patents

Transfering method of nanorod Download PDF

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Publication number
KR101754783B1
KR101754783B1 KR1020150082456A KR20150082456A KR101754783B1 KR 101754783 B1 KR101754783 B1 KR 101754783B1 KR 1020150082456 A KR1020150082456 A KR 1020150082456A KR 20150082456 A KR20150082456 A KR 20150082456A KR 101754783 B1 KR101754783 B1 KR 101754783B1
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layer
nano
nanorod
metal oxide
graphene
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KR1020150082456A
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Korean (ko)
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KR20160147084A (en
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손병혁
서명석
김성수
한창수
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서울대학교산학협력단
고려대학교 산학협력단
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0014—Array or network of similar nanostructural elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B1/00—Nanostructures formed by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B1/001—Devices without movable or flexible elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
    • B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
    • B82B3/0009—Forming specific nanostructures
    • B82B3/0019—Forming specific nanostructures without movable or flexible elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Abstract

A nanorod transfer method is disclosed. According to an embodiment of the present invention, there is provided a method of transferring a nano-rod, comprising the steps of: (a) preparing a substrate having an intermediate layer formed thereon; (b) forming a graphene layer on the intermediate layer; (c) forming a layer of a diblock copolymer on the graphene layer; (d) forming a nano-rod pattern on the double-block copolymer layer; (e) forming a metal oxide nanorod within the nanorod pattern; (f) removing the double-block copolymer layer; (g) separating the graphene layer having the metal oxide nanorods formed thereon from the substrate by etching the intermediate layer; And (h) attaching a lower portion of the graphene layer to a surface of a predetermined material.

Description

{TRANSFERING METHOD OF NANOROD}

The present invention relates to a nanorod transfer method. More particularly, the present invention relates to a transfer method capable of forming a nanorod on a graphene layer and transferring the nanorod treated with the super-hydrophobicity so that the surface of the transferred material becomes super-hydrophobic.

A nanorod refers to a bar structure whose size is in nanometers. Nanorods exhibit electrical, optical, and magnetic properties that differ from typical bulk materials due to quantum mechanical effects in the ultra-micro world.

As a method for producing such a nanorod, there is a method using a double block copolymer nano-template. The process of forming the nano-templates of the double-block copolymers and the process of forming the nano-rods within the nano-templates of the double-block copolymers involve high temperature treatment, the use of corrosive chemicals. However, it is difficult to form a nano-rod by forming a double-block copolymer nano-template on a metal or a flexible substrate. Metal or flexible substrates are highly susceptible to deformation and damage to high temperature, corrosive chemicals.

In addition, when transferring a nanorod to the surface of a specific substance, various applications can be attempted as well as transferring the nanoparticle to the surface of a specific substance. Particularly, by transferring the hydrophobic treated nanorod to the surface of a specific substance, a waterproof electronic device, a moisture removing glass, and the like can be derived. However, in order to transfer the nanorod to the surface of a specific substance, there is a problem that the process becomes complicated, for example, a method of forming a nano-rod after forming the above-mentioned double-block copolymer nano-template on the surface of a specific substance .

On the other hand, graphene is a two-dimensional carbon structure having a thickness of about one atom, which is a planar material composed of bonded carbon atoms in a hexagonal arrangement. Graphene exhibits excellent conductivity and mechanical properties, and has excellent thermal and chemical stability.

Therefore, the present inventors have developed a method for transferring nanorods utilizing graphene which is excellent in thermal and chemical stability.

It is an object of the present invention to provide a nanorod transfer method capable of easily transferring a nanorod to a surface of a specific material.

It is another object of the present invention to provide a nanorod transfer method capable of realizing a super-hydrophobic surface by transferring a nanorod subjected to a hydrophobic treatment to a surface of a specific material.

According to an aspect of the present invention, there is provided a method of transferring nanorods, comprising: (a) preparing a substrate having an intermediate layer formed thereon; (b) forming a graphene layer on the intermediate layer; (c) forming a layer of diblock copolymer on the graphene layer; (d) forming a nano-rod pattern on the double-block copolymer layer; (e) forming a metal oxide nanorod within the nanorod pattern; (f) removing the double block copolymer layer; (g) separating the graphene layer having the metal oxide nanorods formed thereon from the substrate by etching the intermediate layer; And (h) attaching a lower portion of the graphene layer to a surface of a predetermined material.

The graphene layer may comprise a graphene oxide or a reduced graphene oxide.

The double block copolymer layer may comprise a polystyrene-polymethylmethacrylate (PS-PMMA) diblock copolymer.

The metal oxide nanorod may be a titanium dioxide (TiO 2 ) nanorod.

(d) comprises: (d1) phase-separating the double-block copolymer layer into a first block and a second block by heat treatment; And (d2) applying UV to remove the second block of the double-block copolymer to form a nano-rod pattern.

(e) comprises the steps of: (e1) immersing a double-block copolymer layer in which a nanorod pattern is formed in a metal oxide-containing solution; And (e2) forming a metal oxide nanorod within the nanorod pattern.

The metal oxide containing solution may be a solution of titanium isopropoxide isopropanol.

between the step (d) and the step (e), hydrophilicity of the surface of the double-block copolymer layer having the nano-rod pattern formed thereon may be modified.

The surface of the double block copolymer layer can be modified to be hydrophilic by oxidative plasma treatment.

Step (f) can be removed by calcining the double-block copolymer layer

between step (f) and step (g), (f ') hydrophobic treatment of the metal oxide nanorod; And forming a support layer for supporting the graphene layer so that the graphene layer is not decomposed on the graphene layer on which the metal oxide nanorod is formed on the (f ").

(f ') comprises the steps of: (f'1) immersing the metal oxide nanorods in an OTS toluene solution, followed by drying; And (f'2) heating the metal oxide nanorod.

The intermediate layer may comprise silicon oxide.

The support layer may comprise polymethylmethacrylate (PMMA).

(i) removing the support layer.

further comprising the step of modifying the surface of the graphene layer using a crosslinkable random copolymer between step (b) and step (c), wherein the crosslinkable random copolymer comprises poly (styrene-methyl methacrylate rate-vinyl benzo cycloalkyl butyn) [poly [styrene- ran - ( methyl methacrylate) - ran - (vinyl benzocyclobutene)], P (Sr-MMA-VBC)], or poly (styrene-methyl methacrylate-glycidyl methacrylate) [Poly [styrene- ran - ( methyl methacrylate) - ran - (glycidyl methacrylate)], P (Sr-MMA-GMA)] may be.

According to the present invention, nanorods can be easily transferred to the surface of a specific substance.

Further, according to the present invention, a hydrophobic surface can be realized by transferring the nanorod subjected to the hydrophobic treatment to the surface of a specific substance.

FIGS. 1 to 8 illustrate a process of manufacturing and transferring a nano-rod according to an embodiment of the present invention.
9 is a SEM (scanning electron microscope) photograph showing a nano-rod pattern of a double-block copolymer layer according to an embodiment of the present invention.
10 is a SEM photograph showing a nanorod on a graphene layer according to an embodiment of the present invention.
11 is an optical microscope photograph for testing the superhydrophobicity of a nanorod according to an embodiment of the present invention.
12 is a SEM photograph showing a transferred nanorod on a PET substrate according to an embodiment of the present invention.
13 is an optical microscope photograph showing a nanorod transferred onto various materials according to an embodiment of the present invention.
14 is a graph showing a transmission spectrum of a graphene layer formed on a nano rod according to an embodiment of the present invention.

The following detailed description of the invention refers to the accompanying drawings, which illustrate, by way of illustration, specific embodiments in which the invention may be practiced. These embodiments are described in sufficient detail to enable those skilled in the art to practice the invention. It should be understood that the various embodiments of the present invention are different, but need not be mutually exclusive. For example, certain features, structures, and characteristics described herein may be implemented in other embodiments without departing from the spirit and scope of the invention in connection with an embodiment. It is also to be understood that the position or arrangement of the individual components within each disclosed embodiment may be varied without departing from the spirit and scope of the invention. The following detailed description is, therefore, not to be taken in a limiting sense, and the scope of the present invention is to be limited only by the appended claims, along with the full scope of equivalents to which such claims are entitled, if properly explained. In the drawings, like reference numerals refer to the same or similar functions throughout the several views, and length and area, thickness, and the like may be exaggerated for convenience.

Hereinafter, preferred 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.

1 to 8 are views illustrating a process of manufacturing and transferring the nano-rod 310 according to an embodiment of the present invention.

Referring to FIG. 1, a substrate 100 is prepared. The substrate 100 is preferably made of a silicon material, but is not limited to a material having heat resistance at a temperature of 350 ° C or higher.

An intermediate layer 110 may be formed on the substrate 100. The intermediate layer 110 is formed to easily separate the substrate 100 from the graphene layer 200 by etching in a subsequent process, and is preferably made of silicon oxide. Since the graphene is more adhesive to silicon oxide than the silicon substrate 100, it is advantageous to form the graphene layer 200 on the silicon oxide intermediate layer 110.

Next, referring to FIG. 2, a graphene layer 200 may be formed on the intermediate layer 110. The graphene layer 200 may comprise graphene oxide (GO) or reduced graphene oxide (rGO).

The graphene layer 200 is formed on the intermediate layer 110 by using a thin film forming method such as spin coating in which a dispersion liquid in which graphene oxide (GO) or reduced oxide graphene (rGO) is dispersed in water or the like .

Next, referring to FIG. 3 (a cross-sectional side view of FIG. 3A and a perspective view of FIG. 3B), a diblock copolymer layer 300 is formed on the graphene layer 200 can do. The double block copolymer layer 300 can be formed on the graphene layer 200 by using a thin film forming method such as spin coating with polystyrene-polymethylmethacrylate (PS-PMMA). The double block copolymer layer 300 may be formed to have a thickness substantially equal to the length of a nano rod to be manufactured. PS-PMMA can use PS (150) -PMMA 57, PS (46) -PMMA 21, PS 80 -PMMA 80, PS 5 -PMMA 5, Molecular weight M n , kg mol -1 ].

The surface of the graphene layer 200 is modified by using a crosslinkable random copolymer so that a vertical nanodomain can be formed on the graphene layer 200 before the double block copolymer layer 300 is formed . Random copolymer is cross-linkable poly (styrene-methyl methacrylate-vinyl benzo cycloalkyl butyn) [Poly [styrene- ran - ( methyl methacrylate) - ran - (vinyl benzocyclobutene)], P (Sr-MMA-VBC)], to use a poly (styrene-methyl methacrylate-glycidyl methacrylate) [(glycidyl methacrylate)], P (Sr-MMA-GMA) poly [styrene- ran - (methyl methacrylate) - - ran] desirable.

Next, the nano-rod pattern P may be formed on the double-block copolymer layer 300. The nano-rod pattern 320 is formed by a first block 310 (for example, a PS block) and a second block 320 (for example, a PMMA block), which are polymer blocks constituting a double block copolymer layer, (micro phase separation) may be used. The first block 310 and the second block 320 are self-assembled so that the second block 320 can maintain the cylindrical shape have.

Then, ultraviolet rays are applied to the second block 320, so that only the second block 320 can be selectively removed, and the nano-rod pattern P can be formed.

Next, referring to FIG. 4 (a cross-sectional view of FIG. 4A and a perspective view of FIG. 4B), the metal nano-rod 410 may be formed in the nano-rod pattern P.

If the double-block copolymer layer 310 (or the entire substrate on which the double-block copolymer layer 310 is formed) on which the nano-rod pattern P is formed is immersed in the metal oxide-containing solution, A metal oxide layer 400 may be formed. The metal oxide layer 400 includes a metal oxide nano rod 410 formed in the nano rod pattern P as the metal oxide solution is introduced into the nano rod pattern P and a metal oxide nano rod 410 formed on the double block copolymer layer 310. [ And a cover layer 420. The metal oxide cover layer 420 may be removed according to an etching process described below.

The metal oxide-containing solution is preferably a solution of TTIP [Ti (OCH (CH 3 ) 2 ) 4 ] isopropanol, and the metal oxide nanorod formed thereby is a titanium dioxide (TiO 2 ) desirable. Also, Zn (NO 3) 2 (zinc nitrate) O by using the isopropanol solution to form a zinc oxide (ZnO) nanorods oxide or, Fe (NO 3) 3 (ferric nitrate) O by using the isopropanol solution of iron oxide (Fe x O y ) nanorods.

On the other hand, it is preferable that the surface of the double-block copolymer layer 310 on which the nano-rod pattern P is formed is hydrophilically modified so that the metal oxide-containing solution can be easily introduced into the nano-rod pattern P. By treating the oxygen plasma for several seconds, the surface of the double block copolymer layer 310 can be modified to be hydrophilic.

Next, referring to FIG. 5 (a cross-sectional side view of FIG. 5A and a perspective view of FIG. 5B), the double-block copolymer layer 310 can be removed. The double block copolymer layer 310 can be removed by calcination at a temperature of about 400 ° C for a few tens of minutes.

Then, selectively performing CF 4 plasma etching only on the metal oxide cover layer 420, the metal oxide cover layer 420 is removed from the metal oxide layer 400, and as shown in FIG. 5, Gt; 410 < / RTI >

Next, referring to FIG. 6 (a cross-sectional view of FIG. 6A and a perspective view of FIG. 6B), the intermediate layer 110 is removed by etching to form a metal nano- The graphene layer 200 and the substrate 100 can be separated from each other. The intermediate layer 110 may be etched using HF, NaOH, KOH solution or the like.

Before the intermediate layer 110 is etched, the metal oxide nanorods 410 may be subjected to a hydrophobic treatment. The hydrophobic treatment is performed by immersing the metal oxide nanorods 410 (or the entire substrate on which the metal oxide nanorods 410 are formed) in an OTS toluene solution, drying, Followed by heating.

The present invention is advantageous in that the metal oxide nanorods 410 having hydrophobicity can be produced by subjecting the metal oxide nanorods 410 to hydrophobic treatment. The water droplets on the upper surface on which the plurality of metal oxide nanorods 410 are arranged are difficult to penetrate into the inside of the metal oxide nanorods 410. That is, the arrangement of the metal oxide nanorods 410 may have a predetermined hydrophobicity. This is due to the surface tension to keep water droplets small on the upper surface where the metal oxide nanorods 410 having a structure longer than the horizontal direction are arranged. In addition, the surface of the metal oxide nanorod 410 is subjected to a hydrophobic treatment, which is advantageous in that it can provide super-hydrophobic properties.

6, the support layer 500 may be formed on the graphene layer 200 on which the metal oxide nanorods 410 are formed. The support layer 500 is adhered to the graphene layer 200 to support the graphene layer 200 and the metal oxide nanorod 410 when the substrate 100 and the graphene layer 200 are separated from each other, ) From being decomposed. The support layer 500 is preferably made of polymethylmethacrylate (PMMA).

Next, referring to FIG. 7 (a cross-sectional side view of FIG. 7A and a perspective view of FIG. 7B), the lower portion of the graphene layer 200 can be attached to the surface of a predetermined material 600 . The predetermined material 600 may refer to any material to which the metal oxide nanorod 410 is applied, such as a metal thin film, a polymer substrate, a flexible substrate, an electronic device, or a glass. Attaching to the surface of a predetermined material 600 may be performed by simply transferring the graphene layer 200 onto the predetermined material 600, or by attaching a predetermined adhesive or the like.

Next, referring to Fig. 8 (a cross-sectional side view of Fig. 8A and a perspective view of Fig. 8B), the support metal layer 500 is removed with acetone or the like, The transferring process to the surface of the material 600 can be completed.

(Experimental Example)

Hereinafter, an experiment related to the transfer of the metal oxide nano-rod 410 will be described with reference to FIGS. 9 to 14. FIG.

First, a silicon substrate 100 on which a silicon oxide intermediate layer 110 having a thickness of 300 nm was formed was prepared. Next, oxidized graphene (GO) was synthesized using Hummer's method, and the synthesized graphene oxide (GO) was dispersed in water to obtain a dispersion of 0.1 wt%. The process of coating this on the silicon oxide intermediate layer 110 by spin coating at a rate of 2000 rpm for 30 seconds was repeated five times to form a graphene layer 200 containing oxidized graphene (GO). Then, the graphene layer 200 was dried at a temperature of 40 ° C. for 10 hours in a vacuum state, and then treated with hydrazine vapor at 180 ° C. for 24 hours to form reduced oxidized graphene (rGO) having a thickness of about 2.3 nm The graphene layer 200 including the graphene layer 200 was finally produced. The reduced graphene graphene (rGO) has an advantage that graphene characteristics can be exerted better by removing a portion that can act as a defect such as -O and -OH in the graphene graphene GO.

Then, a 0.5 wt% toluene solution of a crosslinkable random copolymer [P (Sr-MMA-r-VBC)] was spun to modify the surface of the graphene layer 200 containing reduced oxidized graphene Lt; RTI ID = 0.0 > 180 C < / RTI > for 24 hours in a vacuum.

Then, PS-PMMA containing PS molecular weight of 46,000 g / mol and PMMA molecular weight of 21,000 g / mol was spin-coated on the graphene layer 200 at a rate of 4000 rpm for 60 seconds to form a double block copolymer layer 300).

Then, the dual block copolymer layer 300 was heat-treated at a temperature of 230 DEG C for 4 hours in vacuum to separate the PS block 310 and the PMMA block 320 from each other.

Then, ultraviolet rays having a wavelength of 254 nm in a vacuum were applied for 2 hours and rinsed with acetic acid to prepare a porous nano template in which the PMMA block 320 was removed (or a nano rod pattern (P) was formed).

9 is a SEM (scanning electron microscope) photograph showing a nano-rod pattern P of the double-block copolymer layer 310 according to an embodiment of the present invention. 9 is an SEM image obtained by obliquely observing the double-block copolymer layer 310. FIG. The scale bar in Fig. 9 is 200 nm. Referring to FIG. 9, it can be confirmed that the nano-rod pattern P is formed in the double-block copolymer layer 300 in a regular hexagonal array at the nanometer level.

Then, an oxygen plasma (40 mTorr, 80 W) was treated for 3 seconds in order to modify the surface of the double-block copolymer layer 310 formed with the nano-rod pattern P to be hydrophilic.

Subsequently, the entire substrate on which the double-block copolymer layer 310 was formed in the 0.8 M TTIP isopropanol solution was dip-coated to form the metal oxide layer 400 on the entire surface of the double-block copolymer layer 310.

Subsequently, the double-block copolymer layer 310 was removed by calcination at a temperature of 400 ° C. for 30 minutes.

Subsequently, CF 4 plasma etching is selectively performed only on the metal oxide cover layer 420 to remove the metal oxide cover layer 420 from the metal oxide layer 400 and to remove the metal oxide nano-rod 410 from the graphene layer 200 ). ≪ / RTI >

10 is a SEM photograph showing a nanorod 410 on a graphene layer 200 according to an embodiment of the present invention. 10 is an SEM image obtained by obliquely arranging the titanium dioxide nanorods 410. FIG. The scale bar in Fig. 10 is 200 nm. Referring to FIG. 10, it can be confirmed that the titanium dioxide nanorods 410 are formed in a regular hexagonal array on the graphene layer 200.

Then, the titanium dioxide nanorod 410 was immersed in a 0.01 M OTS toluene solution for 10 minutes, washed with anhydrous ethanol, and dried in a nitrogen atmosphere. After the hydrophobic treatment was completed by heating at 120 ° C for 1 hour in air, a superhydrophobic titanium dioxide nanorod 410 was prepared.

11 is an optical microscope photograph for testing the superhydrophobicity of the nano-rod 410 according to an embodiment of the present invention. 11 (a) is a photograph in which water droplets are dropped on the titanium dioxide nanorod 410, and FIG. 11 (b) is a photograph of water droplets rolling when the substrate 100 is tilted by about 10 to be. 11 (a), it can be seen that the static contact angle of the water droplet is 153 degrees. Referring to FIG. 11 (b), even if the inclination of the substrate 100 is about 10 degrees, It can be confirmed that the titanium dioxide nanorod 410 has a super-hydrophobic property.

Then, a PMMA toluene solution containing PMMA molecular weight of 81,000 g / mol was coated on the graphene layer 200 to form the support layer 500.

Subsequently, the silicon oxide intermediate layer 110 was etched with 20% HF solution, and the array of titanium dioxide nanorods 410 supported by the PMMA support layer 500 and the graphene layer 200 were floated on water. The material floating on the water was transferred to a copper foil, a PET flexible substrate (the predetermined material 600).

The PMMA support layer 500 was then removed while rinsing with acetone.

12 is an SEM photograph showing a nanorod 410 transferred on a PET substrate 600 according to an embodiment of the present invention. 12 is an SEM image obtained by obliquely arranging the titanium dioxide nanorods 410. FIG. The scale bar in Fig. 12 is 200 nm. Referring to FIG. 12, it can be confirmed that the shape and quality of the graphene layer 200 and the nanorods 410 are not damaged in the same manner as in FIG. 10, and have regular hexagonal arrangements.

13 is an optical microscope photograph showing a nanorod transferred onto various materials according to an embodiment of the present invention. 13 shows that the graphene layer 200 on which the nano-rods 410 are formed is transferred onto PET, copper foil or another silicon oxide substrate in this order. The nano-rod 410 can be easily transferred onto various materials 600 as shown in FIG. 13, and it can be confirmed that the super-hydrophobic property can be maintained.

FIG. 14 is a graph showing a transmission spectrum of a graphene layer 200 formed on a nano-rod 410 according to an embodiment of the present invention. Referring to FIG. 14, it can be seen that the transmittance of the graphene layer 200 formed with the nano-rod 410 of the present invention is 90% or more, and that even when the material 600 is transferred, the graphene layer 200 has optical transparency. This is possible because of the use of high transmittance graphene and titanium dioxide.

As described above, according to the present invention, the nano-rod 410 can be easily transferred to the surface of the specific material 600 by using the graphene layer 200 as a base layer. In addition, by transferring the nanorods 410 subjected to the hydrophobic treatment to the surface of the specific material 600, a super-hydrophobic surface can be realized.

While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is clearly understood that the same is by way of illustration and example only and is not to be taken in conjunction with the present invention. Variations and changes are possible. Such variations and modifications are to be considered as falling within the scope of the invention and the appended claims.

100: substrate
110: middle layer
200: graphene layer
300: double block copolymer layer
310: first block
320: second block
400: metal oxide layer
410: metal oxide nanorod
420: metal cover layer
500: support layer
600: a predetermined substance
P: Nano-rod pattern

Claims (16)

(a) preparing a substrate on which an intermediate layer is formed;
(b) forming a graphene layer on the intermediate layer;
(c) forming a layer of diblock copolymer on the graphene layer;
(d) forming a nano-rod pattern on the double-block copolymer layer;
(e) forming a metal oxide nanorod within the nanorod pattern;
(f) removing the double block copolymer layer;
(f ') treating the metal oxide nanorod with a hydrophobic treatment;
forming a support layer for supporting the graphene layer on the graphene layer on which the metal oxide nanorod is formed on the surface (f ") so that the graphene layer is not decomposed;
(g) separating the graphene layer having the metal oxide nanorods formed thereon from the substrate by etching the intermediate layer; And
(h) attaching a lower portion of the graphene layer to a predetermined material surface
/ RTI > The method of claim 1, The method according to claim 1,
Wherein the graphene layer comprises a graphene oxide or a reduced graphene oxide. The method according to claim 1,
Wherein the double block copolymer layer comprises polystyrene-polymethylmethacrylate (PS-PMMA) diblock copolymer. The method according to claim 1,
Wherein the metal oxide nanorod is any one of a titanium dioxide (TiO 2 ) nano-rod, a zinc oxide (ZnO) nano-rod, or an iron oxide (Fe x O y ) nano-rod. The method according to claim 1,
(d)
(d1) phase-separating the double-block copolymer layer into a first block and a second block by heat treatment; And
(d2) applying UV to remove the second block of the block copolymer to form a nanorod pattern;
/ RTI > The method of claim 1, The method according to claim 1,
(e)
(e1) immersing a double-block copolymer layer in which a nano-rod pattern is formed in a metal oxide-containing solution; And
(e2) forming a metal oxide nano-rod in the nano-rod pattern
/ RTI > The method of claim 1, The method according to claim 6,
Metal containing solution oxide is TTIP [Ti (OCH (CH 3 ) 2) 4] isopropanol (titanium isopropoxide isopropanol) solution, Zn (NO 3) 2 isopropanol solution, or Fe (NO 3) 3 (ferric nitrate) isopropanol Solution, wherein the nanorod is transferred to the nanorod. The method according to claim 1,
Between step (d) and step (e)
(d ') hydrophilically modifying the surface of the double-block copolymer layer having the nano-rod pattern formed thereon. 9. The method of claim 8,
Wherein the surface of the double block copolymer layer is subjected to oxidative plasma treatment to modify it to be hydrophilic. The method according to claim 1,
wherein step (f) removes the double block copolymer layer by calcination. delete The method according to claim 1,
(f ') comprises:
(f'1) immersing the metal oxide nanorod in an OTS toluene solution and then drying it; And
(f'2) heating the metal oxide nanorod
/ RTI > The method of claim 1, The method according to claim 1,
Wherein the intermediate layer comprises silicon oxide. The method according to claim 1,
Wherein the support layer comprises polymethylmethacrylate (PMMA). 15. The method of claim 14,
(i) removing the support layer
Wherein the nano-imprinting method further comprises: The method according to claim 1,
Between the step (b) and the step (c)
(b ') modifying the surface of the graphene layer using a crosslinkable random copolymer
Further comprising:
Random copolymer is cross-linkable, poly (styrene-methyl methacrylate-vinyl benzo cycloalkyl butyn) [Poly [styrene- ran - ( methyl methacrylate) - ran - (vinyl benzocyclobutene)], P (Sr-MMA-VBC)] , or poly (styrene-methyl methacrylate-glycidyl methacrylate) [poly [styrene- ran - ( methyl methacrylate) - ran - (glycidyl methacrylate)], P (Sr-MMA-GMA)] a, nano Load transfer method.
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Citations (1)

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