KR20120123183A - Method for manufacturing nano-particle array of monodispersity having tunable size, nano-particle array manufactured by the same and the application thereof - Google Patents

Abstract

PURPOSE: A manufacturing method of mono-dispersible nano particle array, a nano-particle array manufactured by the same and applications thereof are provided to evaporating the mono-dispersible nano-particle array by using a block copolymer lithography mode. CONSTITUTION: A manufacturing method of mono-dispersible nano particle array comprises the following step: combining metal ion to a polymer by contacting the polymer to the metal ion. The polymer is a block copolymer of two or more polymers. One or more block copolymers has electric charge opposite to the metal self-assembling the block copolymer; dipping the block copolymer in the metal ion solution; combining the polymer with the metal ion in the metal ion solution; and removing the block copolymer.

Description

Method for manufacturing nano-particle array of monodispersity having tunable size, nano-particle array manufactured by the same and the application

The present invention relates to a method for producing a monodisperse nanoparticle array having a size control, and to a nanoparticle array and its application, and more particularly to a method for producing a monodisperse nanoparticle array can be adjusted in size, the nanoparticles It relates to particle arrays and their applications.

Nanoscale particles have a large surface area resulting from nanoscale quantum confinement effects and small sizes, from which they exhibit size-dependent electrical, magnetic, chemical, optical, and catalytic properties. Patterning nanoparticles into two-dimensional (2D) arrays is already under considerable research due to their potential applications in sensors, magnetic data reservoirs, flash memories, and catalysts. However, despite active research in nanoparticle synthesis, the technique of precisely positioning, aligning and immobilizing nanoparticles on a desired substrate remains a technical challenge. In addition, it is very important to arrange nanopatterned particles on a desired substrate in a controlled manner. If the accuracy of the technique of locating and arranging nanoparticles is high, a nanoparticle array with controlled size can be applied to the various applications described above. Because it can.

Block copolymer lithography is evolving into lithography technology to overcome the inherent resolution limitations of conventional photolithography processes. The horizontal self-assembly technique of the separated block copolymer nanodomains of the microphase allows the fabrication of nanolithography masks that repeat at a size of 30 nm or less on any large area. Furthermore, recent self-assembly and orientation techniques using external electric field application, chemical or topography prepattern methods have achieved nano-patterns arranged horizontally over large areas. However, the inherent polydispersity of self-assembled nanoregions remains a technical challenge for producing nanopatterned morphologies with monodispersity. Moreover, scaled pattern transfer techniques have not been achieved on a block copolymer lithography basis to date.

Accordingly, the problem to be solved by the present invention is to provide a method for producing a nanoparticle array having a monodisperse property and controllable in size on a substrate and a nanoparticle array produced thereby.

Another problem to be solved by the present invention is to provide an application method using a nanoparticle array of monodisperse properties.

In order to solve the above problems, the present invention comprises the step of contacting a metal ion solution with a charged polymer that electrostatically bonds with the metal ion in the solution, comprising the step of coupling the metal ion to the polymer It provides a method for producing a nanoparticle array characterized in.

According to an embodiment of the present invention, the polymer is a block copolymer of two or more polymers, and at least one of the block copolymers has a charge opposite to the metal ion in the solution.

In one embodiment of the invention, the method comprises the steps of self-assembling the block copolymer; Immersing the self-assembled block copolymer in the metal ion solution; Coupling the metal ion and the metal ion with an electrostatic force in the metal ion solution opposite to the metal ion; And it provides a nanoparticle array manufacturing method comprising the step of removing the block copolymer.

One embodiment of the present invention is a method for producing a nanoparticle array using a block copolymer comprising a first polymer and a second polymer, the method comprising the steps of: self-assembling the block copolymer; Selectively bonding the first polymer of the self-assembled block copolymer and the metal ion of the nanoparticle to be deposited by electrostatic interaction; And it provides a method for producing a nanoparticle array using a block copolymer, characterized in that it comprises the step of removing the block copolymer.

In one embodiment of the present invention, the second polymer and the metal ion do not electrostatically interact.

In one embodiment of the present invention, the selective binding of the metal ions proceeds by dipping the self-assembled block copolymer in the solution containing the metal ion, the metal ion is in the form of a metal complex compound of the anion, The first polymer is cationic in the aqueous solution.

In one embodiment of the invention, the first polymer comprises nitrogen and the aqueous solution is in an acidic condition of pH <7.

In one embodiment of the present invention, the block copolymer is characterized in that the poly (styrene-block-4-vinylpyridine).

The present invention provides a method for producing a nanoparticle array, characterized in that the heterogeneous nanoparticles are laminated on a substrate according to the above-described method.

The present invention provides a nanoparticle array produced by the above method.

The present invention provides a method for producing carbon nanotubes comprising growing carbon nanotubes using the above-described nanoparticle array as a catalyst.

The present invention comprises the steps of applying a polystyrene-block-poly (4-vinylpyridine) (PS-b -P4VP) thin film on the substrate, followed by spin coating; Self-assembling the thin film; Dipping the self-assembled thin film in a solution containing an anion metal complex; And it provides a method for producing a nanoparticle array using a block copolymer, characterized in that it comprises a step of removing the thin film.

In one embodiment of the present invention, the solution comprises HCl, the pyridine group nitrogen of the thin film immersed in the solution is protonated, the metal complex is K3 [Fe (CN) ₆ ], the prepared nanoparticles Is iron oxide particles.

In one embodiment of the present invention, the method further includes the step of reducing the prepared iron oxide particles to produce an iron nanoparticle array.

According to the present invention, monodisperse nanoparticle arrays can be deposited by block copolymer lithography. In addition, since the nanoparticle size can be easily controlled by the loading time of the metal ion, it can be effectively applied to various applications such as a catalyst.

1 is a process schematic diagram according to an embodiment of the present invention.
2 is a process schematic diagram according to another embodiment of the present invention.
3 to 5 are PS-b-P4VP thin film SEM images (FIG. 1B) after spin on a silicon substrate, and PS-b-P4VP thin film images (FIG. 1C, 1D) after solvent-annealing.
6 to 8 are SEM images of Fe 2 O 3 nanoparticle arrays prepared by immersing a spincast-solvent annealed block copolymer template in an aqueous solution containing a metal ion complex for 1 minute.
9-11 are statistical distributions of Fe 2 O 3 nanoparticle diameters.
FIG. 12 is an SEM image showing the growth of an array of nanoparticles obtained from a solvent annealed template for 5 hours with time the template was immersed (loaded) in a metal complex ion solution.
FIG. 13 is a graph illustrating change in diameter of nanoparticles according to metal ion loading time. FIG.
14 is an XPS spectrum of the Fe 2 O 3 nanoparticle array obtained after oxygen plasma treatment.
15 is a cross-sectional SEM image of vertically grown carbon nanotubes.
FIG. 16 is an SEM image of the lower portion of the carbon nanotube at high magnification. FIG.
17 and 18 are SEM images of carbon nanotubes grown from double-walled and triple-walled nanoparticle catalysts.
FIG. 19 is a graph of statistically comparing the number of carbon walls prepared from the block copolymer template in the spin state with the block copolymer template after annealing for 5 hours.
FIG. 20 shows single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), triple-walled carbon nanotubes (TWNTs), and four-walled multi-walled carbon nanotubes (MWNTs) prepared from a 5-hour annealed block copolymer template. The relative fractions of) are analyzed according to the loading time of the complex complex.
FIG. 21 is a schematic diagram of hierarchical patterning of nanoparticle arrays and corresponding carbon nanotube growth. FIG.
22 is a cross-sectional SEM image demonstrating no carbon nanotubes in the etched region.
23 to 25 are SEM images of patterned carbon nanotube arrays prepared from hexagonal and square masks.
26 to 29 illustrate a method of depositing nanoparticles in various forms by a scheme in accordance with the present invention.

Hereinafter, an item usage period control method and a server therefor will be described with reference to the accompanying drawings.

In the following description, in order to clarify the understanding of the present invention, description of well-known technology for the features of the present invention will be omitted. The following embodiments are detailed description to help understand the present invention, and it should be understood that the present invention is not intended to limit the scope of the present invention. Therefore, equivalent inventions that perform the same functions as the present invention will also fall within the scope of the present invention.

In the following description, the same reference numerals denote the same components, and unnecessary redundant explanations and descriptions of known technologies will be omitted.

The terms "comprise", "comprise" or "having" described above mean that a corresponding component may be included unless specifically stated otherwise, and thus does not exclude other components. It should be construed that it may further include other components. All terms, including technical and scientific terms, have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs, unless otherwise defined. Commonly used terms, such as predefined terms, should be interpreted to be consistent with the contextual meanings of the related art, and are not to be construed as ideal or overly formal, unless expressly defined to the contrary.

The foregoing description is merely illustrative of the technical idea of the present invention, and various changes and modifications may be made by those skilled in the art without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed in the present invention are intended to illustrate rather than limit the scope of the present invention, and the scope of the technical idea of the present invention is not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings. The following embodiments are provided as examples to ensure that the spirit of the present invention can be fully conveyed to those skilled in the art. Therefore, the present invention is not limited to the embodiments described below, but may be embodied in other forms.

The present invention provides a method for achieving monodisperse nanoparticle arrays that can be scaled to sub-nanometer levels directly from block copolymer lithography in order to solve the above problems. The present invention produces monodisperse nanoparticle arrays on a substrate, in particular by inducing an electrostatic interaction between a polymer and a metal ion of any of the self-assembled block copolymers. The interaction of block copolymers with metal ions in the present invention has a very high specificity (because electrostatic interactions only occur for certain block polymers of limited size) and are oriented in a specific direction with metal deposition. Monodispersed nanoparticle arrays can be deposited to a desired size, depending on the uniformity of the block copolymer morphology of the structure.

The method for producing a nanoparticle array according to the present invention produces a nanoparticle array using a block copolymer comprising at least two different types of polymers, namely, a first polymer and a second polymer, as described above. The copolymer is self-assembled to prepare a block copolymer template having a specific structure, and the metal ions of the specific polymer (first polymer) in the self-assembled block copolymer template and the nanoparticles to be prepared are subjected to electrostatic interaction. Selectively bind and remove the block copolymer again. In the case of the present invention, the block copolymer is used as a template for preparing nanoparticle arrays, and in particular, the present invention specifically binds the self-assembled first polymer and precursor solution ions of nanoparticles (metal nanoparticles). To prepare a nanoparticle array. Therefore, according to one embodiment of the present invention, the selective bonding between the base metal ion and the first polymer proceeds in such a way that the self-assembled block copolymer is immersed in the solution containing the metal ion. The metal ion is in the form of an anionic metal complex and the first polymer bears a cation in the aqueous solution. In an embodiment of the present invention, a polymer having a cation-containing nitrogen-containing group (for example, pyridine) bound by protonation under weak acid conditions such as HCl is used as the first polymer, and an anion containing a metal such as Fe is used. A metal nanoparticle array obtained from metal ions, which is bound to the first polymer and is then removed, can be obtained.

1 is an overall schematic diagram of a process according to an embodiment of the present invention.

Referring to Figure 1, the amphiphilic poly (styrene-block-4-vinylpyridine) (PS-b-P4VP) on any substrate (PS block (second polymer) is 24.0 kg / mol, P4VP block ( 1 polymer) was mixed with a 9.5 kg / mol) block copolymer thin film in a toluene: tetrahydrofuran (THF) mixed solution, spin-cast and immediately self-assembled to form a P4VP nanocylinder array perpendicular to the PS matrix. , Self-assembled structure was formed. The solvent was then annealed in toluene, with the THF mixed vapor slowly ordering the cylindrical nanoregions sideways over time. With this horizontal arrangement, the size of the self-assembled cylinder region structure was fairly uniform. Thus, following an annealing of about 5 hours, a horizontally-array hexagonal cylinder array with a very narrow size distribution was produced. As such, the block copolymer thin film having a high order, horizontally arranged nanoarea structure and deposited on the substrate was immersed in a 1 mM K 3 [Fe (CN) 6]: 0.1% HCl aqueous solution. The anionic metal complex of Fe (CN) 6-3 binds to the quantized pyridine nitrogen (cationic) of the P4VP cylinder nanodomain, which is the first polymer. Thereafter, an oxygen plasma treatment was performed on the entire area to remove the organic block polymer template, wherein the monodispersed iron oxide (Fe 2 O 3) nanoparticle array remained at the position of the P4VP cylinder. Depending on the loading time of the iron ion complex on the aqueous solution (ie, contact time), the nanoparticle size can be controlled to be less than nanometers.

The Fe 2 O 3 nanoparticle array prepared according to the present invention may function as a catalytic functional material for carbon nanotube (CNT) growth. However, as well as K 3 [Fe (CN) 6], any other ionic metal complex ion can be used to fabricate and fix various types of metal nanoparticle arrays on any substrate. Furthermore, the following examples of the present invention used one kind of metal ion complex, but when two or more ion complexes are mixed and used, heterogeneous metal nanoparticle arrays are also possible. In addition, when the self-assembly of the block copolymer on the first formed metal nanostructure again and then the second metal is deposited in the same manner, a multilayer dissimilar metal array having a point-point, line-point, and core-shell structure Can be formed.

In another embodiment of the present invention, only a specific block copolymer (P4VP in one embodiment of the present invention) that is protonated in an acidic solution is immersed in an acidic solution, and the specific block is formed by electrostatic action with a metal anion. Precipitates by bonding a metal to it. In this case, various metal layers may be formed according to the form of the substrate. For example, when the copolymer substrate is in the form of a brush, a metal may be bonded to the surface of the brush and a rod-shaped metal layer may grow. In contrast, in the case of a thin film form, since the metal is electrostatically coupled to the entire thin film, the metal layer may be in the form of a film.

2 is a process schematic diagram of a metal layer manufacturing method according to the embodiment of the present invention.

Referring to FIG. 2, a P4VP polymer substrate deposited on a silicon substrate is immersed in an acid solution containing metal anion (M−) to electrostatically bond a metal anion to the polymer substrate charged with a cation, thereby providing the metal Anions are deposited on the polymer substrate. Thereafter, the polymer substrate is removed to prepare a metal layer deposited in a form corresponding to the polymer substrate.

Hereinafter, a method of manufacturing a nanoparticle array and a method of using the same according to an embodiment of the present invention will be described in detail.

Example

matter

Polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP, molecular weight: 24 kg mol-1 PS, 9.5 kg mol-1 P4VP), asymmetric block copolymer, potassium hexacyanoate (III) (Potassium ferricyanide), pure ammonia and acetylene gas were prepared.

Metal Nanoparticle Array Deposition

The silicon wafer was immersed in a piranha solution ((7: 3 H 2 SO 4: H 2 O 2) for 1 hour at 110 ° C. and washed several times with deionized water. Ps-b-P4VP block copolymer (0.5 wt%) was added to the toluene / THF mixture. A 25 nm thick PS-b_P4VP thin film from 0.5 wt% toluene was dissolved and spincoated onto the washed silicon The spinned film was solvent annealed in a small sealed container, first toluene and THF (toluene: THF). 20:80 v / v) A homogeneous mixed solution was introduced into the closed container and the solvent was evaporated spontaneously for several minutes at room temperature (25 2 ° C.) to render the vessel saturated with toluene and THF steam. The volume ratio of was inconsistent with the ratio of the mixed liquor, which is due to the different vapor pressures of toluene and THF, and then the spin film was annealed for 0 to 5 hours, creating a laterally arranged cylindrical nano-zone. The solvent annealed sample was immersed in a 1 mM K 3 [Fe (CN) 6]: 0.1% HCl aqueous solution for a given time (loading time) After metal ion bonding (loading), the sample was washed several times with deionized water, The metal ions were removed, and then dried with nitrogen, and then subjected to oxygen plasma treatment to remove the polymer template to prepare an array of Fe 2 O 3 nanoparticles of iron oxide on a silicon substrate.

Of vertical carbon nanotubes PECVD  Growth method

The present invention selected the catalyst as one of the applications of the prepared nanoparticle array. To this end, the carbon nanotubes were grown by PECVD using the nanoparticle array according to the present invention as a catalyst. In order to grow carbon nanotubes, the substrate on which the Fe 2 O 3 nanoparticle array was prepared was first heated to 600 ° C. while flowing hydrogen and ammonia mixed gas. The hydrogen and ammonia content was 80: 20% by volume and the total mixed gas flow rate was maintained at 100 sccm. As the substrate temperature reached 600 ° C., the substrate was annealed (usually less than 2 minutes) and the Fe 2 O 3 nanoparticles were reduced to Fe metal particles. Thereafter, the chamber pressure was increased to 5 torr, and the direct current plasma proceeded according to the application of the cathode DC voltage of 470V. Next, acetylene gas was slowly flowed at a flow rate of 5 sccm for 1 to 2 minutes to prepare carbon nanotubes grown densely and vertically.

analysis

Block copolymer  Template analysis

3 to 5 are PS-b-P4VP thin film SEM images (FIG. 1B) after spin on a silicon substrate, and PS-b-P4VP thin film images (FIG. 1C, 1D) after solvent-annealing. After spin, it can be seen that the nanocylinders of the P4VP blockpolymer are oriented vertically, which is due to the high directional vapors generated during the spin-cast process. However, it can be seen that the arrangement density in the horizontal direction of the cylinder is not uniform and the size distribution is also wide (see Fig. 3). However, the horizontal orientation and size uniformity of the cylinder is greatly improved after solvent annealing at room temperature in toluene: THF (20:80 v: v). Samples annealed for 2 hours are orderly ordered in a hexagon and exhibit a relatively small grain size (see FIG. 4). Samples annealed for 5 hours show a hexagonal orientation structure with large grain size (see FIG. 5).

Fast Fourier transform (FFT) results illustrate the improvement of the horizontal array structure.

Referring to the above results, six spot spots with strong multiple high order reflection properties indicate that the hexagonal structures arranged in orderly horizontally are densely packaged (inset in FIG. 5).

6 to 8 are SEM images of Fe 2 O 3 nanoparticle arrays prepared by immersing a spincast-solvent annealed block copolymer template in an aqueous solution containing a metal ion complex for 1 minute.

6 to 8, since the P4VP vertical cylinder structure is directly exposed to the water-soluble complex solution, the anionic metal complex easily binds to the quantized pyridine group even in mildly acidic conditions. Thus, the resulting Fe2O3 nanoparticle array accurately replicates the morphology of the block copolymer template. The particles obtained after the spin, or from an insufficiently annealed block copolymer template, have a large particle diameter and a wide size distribution (10.84 nm 2.98 nm after spin, 8.40 nm 1.79 nm after 2 hours annealing). In contrast, nanoparticles obtained from well grown molds have a cylinder structure of small size and narrow size distribution (6.03 nm to 1.0 nm).

6 to 8 are SEM images of Fe 2 O 3 nanoparticle arrays prepared by immersing a spincast-solvent annealed block copolymer template in an aqueous solution containing a metal ion complex for 1 minute.

In addition to the results of FIGS. 6 to 8, Table 1 below summarizes the nanosize characteristics of the block copolymer nano template and the obtained nanoparticle array of FIG. 1.

Block Copolymer Mold Iron Oxide Nanoparticle Array Average diameter (nm) Average center-to-center distance (nm) Average diameter (nm) Average Center-to-Center Distance (nm) After spin 11.04 ± 3.9 24.58 ± 4.6 10.84 ± 2.98 25.38 ± 6.1 2 hours 10.35 ± 2.3 22.39 ± 2.6 8.40 ± 1.79 23.95 ± 4.5 5 hours 9.01 ± 1.2 19.23 ± 1.3 6.03 ± 1.0 19.71 ± 1.7

6 to 8 and Table 1 results, the average diameter of the nanoparticles is somewhat smaller than the block copolymer cylinder diameter, due to the particle density that occurs when the block copolymer is removed by plasma treatment.

Nanoparticle Array Analysis

FIG. 12 is an SEM image showing the growth of an array of nanoparticles obtained from a solvent annealed template for 5 hours with time the template was immersed (loaded) in a metal complex ion solution.

Referring to FIG. 12, the size of monodispersed nanoparticles gradually increases with loading time. Precise control of particle size down to nanometer-sized sizes is possible at relatively low concentrations of aqueous metal complex ions (1 mM K3 [Fe (CN) 6]). The difference in average diameter and height is graphed according to loading time, which is shown in FIG. 13. The growth rate was fast at short loading times but gradually slowed down. The growth behavior may correspond to a typical power law curve, Atα. According to the least square fit, an index α of 0.16 in diameter and 0.39 in height is obtained. These low values are due to the low concentration of metal ions as well as the limited diffusion of metal ions through the P4VP nanosize cylinder. In other words, in the block copolymer template, the PS matrix functions as a barrier to diffusion of metal ions around the P4VP cylinder structure, but the nanoparticles are adsorbed as the loading time gradually increases. 14 is an XPS spectrum of the Fe 2 O 3 nanoparticle array obtained after oxygen plasma treatment. Referring to the result of FIG. 14, the Fe-2p3 / 1 peak of 710.5 eV proves that Fe in the Fe2O3 state is present.

Carbon Nanotube Analysis

The catalytic functionality of monodisperse nanoparticle arrays was analyzed through catalyst-based carbon nanotube growth experiments. Among various carbon nanotube synthesis methods, plasma vapor deposition (PECVD) was used to induce vertically oriented carbon nanotube growth. PECVD enables low temperature growth at temperatures below 600 ° C., which is one of the important conditions for device integration. The Fe 2 O 3 particle array prepared in the present invention is converted into Fe particles by thermal reduction before carbon nanotube growth. That is, vertically oriented carbon nanotubes were prepared with high yield by slowly adding nitrogen, ammonia, and acetylene mixed gas (FIG. 15). Such high yield growth of carbon nanotubes proves the high purity and high functionality of the monodisperse nanoparticle array prepared according to the present invention.

In the present invention, carbon nanotubes having a height of 26.7 μm were grown after one minute under optimum conditions. FIG. 16 is an SEM image of the lower portion of the carbon nanotube at high magnification. FIG. The carbon nanotube diameter is 5.3 nm, which corresponds to 2/3 of the diameter of the catalyst particles of 8.6 nm. 17 and 18 are high-resolution TEM images of carbon nanotubes grown from monodisperse catalyst particles prepared according to the present invention. When the images are analyzed, average diameters of 5.8 and 9.9 nm appear. The narrow distribution of carbon nanotube diameters and the number of carbon walls in the graphite structure is due to the monodisperse nature of the catalyst particles. That is, 88% of the carbon nanotubes grown from the 5.6 nm catalyst particles were double walls, whereas 72% of the carbon nanotubes grown from the 9.9 nm catalyst particles were triple walls (see FIG. 17). FIG. 18 is a statistical comparison of the number of carbon walls prepared from the block copolymer template in the spin state with the block copolymer template after annealing for 5 hours. The loading of the complex ion was maintained at 5 minutes. Since spinned nanoparticle arrays have a wide size distribution, carbon nanotubes grown from them also exhibit a wide carbon wall number distribution. In contrast, the carbon wall numbers of the carbon nanotubes obtained from the blow copolymer templates annealed for 5 hours showed a much narrower distribution. FIG. 19 shows single-walled carbon nanotubes (SWNTs), double-walled carbon nanotubes (DWNTs), triple-walled carbon nanotubes (TWNTs) and four-walled multi-walled carbon nanotubes (MWNTs) prepared from a block copolymer template annealed for 5 hours. The relative fractions of) were analyzed according to the ion complex loading time. The relative fraction of each carbon wall number varied with catalyst size as a function of loading time. In the case of carbon nanotube growth in the NH3 environment, even the smallest particle size, the growth of single-walled carbon nanotubes was suppressed, which is thought to be due to the nitrogen doping effect. In Figure 21, the average diameter of the carbon nanotubes were graphed according to the ion loading time. The growth properties were similar to the catalyst particle growth, which means that the carbon nanotube diameter is closely related to the catalyst particle size.

Size-controlled nanoparticle deposition in accordance with the present invention enables the hierarchical patterning of catalysts and their corresponding carbon nanotube arrays. As shown in FIG. 21, nanoparticle deposition is impossible without block copolymers. In other words, by using an oxygen plasma etching using a mask, it is possible to manufacture carbon nanotubes in a pattern hierarchically, that is, a pattern in which a deposition region and a non-deposition region are clearly distinguished. The resulting vertically aligned carbon nanotubes morphology accurately simulates the etching mask arrangement. 22 is a cross-sectional SEM image demonstrating no carbon nanotubes in the etched region. 23 to 25 are SEM images of patterned carbon nanotube arrays prepared from hexagonal and square masks. Such a hierarchically patterned vertically oriented, carbon nanotube array with adjustable size and number of carbon walls is applicable to applications such as electroluminescent devices in which an electric field occlusion effect occurs due to the proximity characteristics of neighboring tubes.

As described above, the monodisperse nanoparticle array deposition method according to the present invention can be controlled in size, which can be achieved by block copolymer lithography. The vertically aligned cylindrical block copolymer nanoregions are prepared by solvent annealed PS-b-P4VP block copolymer thin films, which are immersed in a water soluble ion metal complex solution, whereby the anionic metal complex is transferred to the P4VP cylinder core. Diffusion, which is achieved by very specific electrostatic interactions. Thus, the specific dispersion of metal ions in nanoscale confined spaces enables the production of monodisperse nanoparticle arrays that are laterally aligned at sub-nanometer levels. In addition, the catalytic functionality of monodisperse nanoparticle arrays was demonstrated through carbon nanotubes grown vertically by catalytic PECVD. The present invention, which controls the catalyst particle size to a size less than nanometers, enables the growth of carbon nanotubes in a vertical orientation, in particular where the number of carbon walls can be selectively determined. It is also possible to align nanoparticle arrays within the trenches through graphoepitaxy. That is, in the case of Graphoepitaxy, since the block copolymer is aligned in the trench formed in the substrate, it is possible to form a nanostructure having a single domain, and to form a single or dissimilar metal array according to various methods described below. Can be formed in the desired trench structure.

26 to 29 illustrate a method of depositing nanoparticles in various forms by a scheme in accordance with the present invention.

Referring to FIG. 26, another heterogeneous metal is deposited on the metal nanoparticle array (first metal array) manufactured according to the present invention in an area other than the first metal array formation region by electrostatic interaction. , Shows a step of manufacturing a nanoparticle thin film composed of two or more types of metal nanopoints spaced apart from each other.

Referring to FIG. 27, first, a block copolymer is raised, followed by solvent annealing or heat treatment to form nanolines parallel to the substrate. After applying the block copolymer again on the formed nano-line again, to form a nano dot by the method according to the invention. As a result, nanodots are located between the spaces of the pre-formed nanoline.

FIG. 28 shows a method of depositing alloy nanopoints of dissimilar metal on a substrate using two kinds of metal precursor solutions together. Even in this case, the dissimilar metal precursor solution must be selectively electrostatically bonded to the self-assembled block copolymer. That is, when loading a metal anion, alloy nanoparticles can be obtained by using a heterogeneous sample, and the properties of the alloy nanoparticles can be observed by heat treatment and recrystallization thereof.

FIG. 29 illustrates a process of depositing nanoparticles of a so-called core-shell structure on a substrate, in which a plurality of nanodot deposition processes according to the present invention are sequentially performed, in which second nanodots are sequentially stacked on a first nanodot. The method is shown.

While the present invention has been described with reference to exemplary embodiments thereof, it will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit and scope of the invention as defined in the appended claims. .

Claims (16)

Contacting a metal ion solution with a charged polymer that electrostatically bonds with the metal ion in the solution, thereby bonding the metal ion to the polymer. The method of claim 1,
The polymer is a block copolymer of two or more polymers, wherein at least one of the block copolymers has a charge opposite to the metal ion in the solution. The method of claim 2, wherein the method
Self-assembling the block copolymer;
Immersing the self-assembled block copolymer in the metal ion solution;
Coupling the metal ion and the metal ion with an electrostatic force in the metal ion solution opposite to the metal ion; And
Method for producing a nanoparticle array comprising the step of removing the block copolymer. Method for producing a nanoparticle array using a block copolymer comprising a first polymer and a second polymer, the method
Self-assembling the block copolymer;
Selectively bonding the first polymer of the self-assembled block copolymer and the metal ion of the nanoparticle to be deposited by electrostatic interaction; And
Method of producing a nanoparticle array using a block copolymer, characterized in that it comprises the step of removing the block copolymer. The method of claim 4, wherein
The second polymer and the metal ion is a nanoparticle array manufacturing method using a block copolymer, characterized in that does not interact electrostatically. The method of claim 4, wherein
Selective bonding of the metal ions is characterized in that the self-assembled block copolymers are immersed in the solution containing the metal ions, characterized in that proceeding, nanoparticle array manufacturing method using a block copolymer. The method according to claim 6,
The metal ion is in the form of an anion metal complex, the first polymer is characterized in that the cation in the aqueous solution, a nanoparticle array using a block copolymer. 8. The method of claim 7,
The first polymer comprises nitrogen, the aqueous solution is characterized in that the acidic conditions of pH <7, nanoparticle array manufacturing method using a block copolymer. The method of claim 4, wherein
The block copolymer is poly (styrene-block-4-vinylpyridine), characterized in that the nanoparticle array using a block copolymer. 10. A method of manufacturing a nanoparticle array, wherein different types of nanoparticles are laminated on a substrate according to the method of claim 4. 10. A nanoparticle array produced by the method according to claim 4. A method for producing carbon nanotubes, comprising growing carbon nanotubes using the nanoparticle array according to claim 11 as a catalyst. Applying a thin film of polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP) onto a substrate, followed by spin coating;
Self-assembling the thin film;
Dipping the self-assembled thin film in a solution containing an anion metal complex; And
Method of manufacturing a nanoparticle array using a block copolymer, characterized in that it comprises the step of removing the thin film. The method of claim 13,
The solution comprises HCl, characterized in that the pyridine group nitrogen of the thin film immersed in the solution is protonated, nanoparticle array manufacturing method using a block copolymer. The method of claim 14,
The metal complex is K 3 [Fe (CN) ₆ ], wherein the prepared nanoparticles are iron oxide particles, nanoparticle array manufacturing method using a block copolymer. 16. The method of claim 15,
The method further comprises the step of reducing the produced iron oxide particles, to produce an iron nanoparticle array, nanoparticle array manufacturing method using a block copolymer.

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