WO2011105822A2 - Method for producing a zinc oxide nanoring structure using a self-assembled diblock copolymer and a sol-gel process - Google Patents

Abstract

The present invention relates to a method for producing a zinc oxide nanoring structure in hybrid form, in which a two-dimensionally arranged ultra-dense zinc oxide nanoring structure and gold nanoparticles are introduced, the method using a self-assembled diblock copolymer and a sol-gel process, to a hybrid zinc oxide nanoring structure in which a zinc oxide nanoring structure produced by the above method and gold nanoparticles are introduced, and to a zinc oxide nanoring structure array in which a hybrid zinc oxide nanoring structure is arranged, the nanoring structure having the zinc oxide nanoring structure or gold nanoparticles introduced onto a substrate.

Description

Method for producing zinc oxide nanoring structure using self-assembled biblock copolymer and sol-gel process

The present application provides a method for manufacturing a hybrid zinc oxide nanoring structure in a hybrid form in which two-dimensional aligned ultra-high density zinc oxide nanoring structures and gold nanoparticles are introduced by using a self-assembled diblock copolymer and a sol-gel process, and The present invention relates to a zinc oxide nanoring structure and a hybrid zinc oxide nanoring structure in which gold nanoparticles are introduced.

Recently, self-assembly technology is in the spotlight as a tool for manufacturing nano-sized devices such as medical, electronic / information, optics, and sensors. For example, two-dimensional or three-dimensional assemblies of monodisperse nanoparticles are widely used in functional coatings, dye-free paints, catalysts, luminescent materials, etc., templates for the growth of arranged micro or nanoporous materials, light splitting , Optical filters, photonic crystals, etc. have been utilized in optical materials and device applications.

The diblock copolymer tends to phase-separate each block into its respective domain due to the restriction of the covalent linkage point between the two blocks in the form of two or more polymer chains covalently linked through one end. Such a biblock copolymer can form a periodic nanostructure having a size of about 10 nm to 100 nm by spontaneous phase separation, the shape and size of the nanostructure is the molecular weight of the biblock copolymer, It is determined by the volume ratio, the Flory-Huggins interaction coefficient between blocks, and further, by dissolving in a solvent selective to one block, spherical and cylindrical micelles of spontaneous size can be spontaneously formed.

Using the self-assembly of the biblock copolymer as described above, the size of the particles in the nanostructure of the diblock copolymer can be limited to nanometer size without any treatment, and the arrangement of the particles is also the size of the nanostructure Limited by the and spacing, the size and arrangement of the particles can be controlled.

Zinc oxide has a wide bandgap of 3.3 eV at room temperature, and has a large exciton binding energy of 60 meV, which is greater than the thermal energy of 24 meV, thereby facilitating light emission in the ultraviolet region. Because of its excellent optical properties, zinc oxide has attracted much attention as an optical device such as an ultraviolet light emitting diode (Ultraviolet LED) or a laser diode (LD). Especially, zinc oxide nanostructures are used in optoelectronic devices, ultraviolet laser devices, chemical sensors, and solar cells. Increasingly, interest is amplified by the potential applications in photocatalysts.

The zinc oxide of the nanostructure may be prepared by ion implantation, sputtering, sol-gel process, photoreduction reaction, etc., but it is not advantageous in terms of economics because most of them require expensive equipment or adopt a complicated multi-step process. In addition, when manufacturing the multi-component particles have a disadvantage in that the uniformity of the components in the particles, and difficult to control in the form of the particles.

On the other hand, the sol-gel process, which is a liquid phase method, is capable of mixing and preparing raw materials at the molecular level, thereby increasing uniformity of the prepared particles, preparing particles having a large surface area, and lowering the sintering temperature. Therefore, it has been widely used in the preparation of multicomponent composites. In particular, the sol-gel process using a high-purity alkoxide hydrolysis has a wide range of applications, there is an advantage that the final product can be produced in various forms such as powder, monolith, fiber form.

The present inventors have completed the present application by studying a novel manufacturing method that can produce a zinc oxide nanoring structure using a self-assembly diblock copolymer and a sol-gel process. In particular, the effects of specific components of the sol-gel precursors on the self-assembly of self-assembled diblock copolymers and the formation of nanoring structures were studied. In addition, the molecular weight or relative volume fraction of the diblock copolymer and zinc oxide sol It was found that the shape and arrangement of the nanoring structure can be controlled by varying the concentration of the gel precursor, and further, the production of the hybrid type gold-zinc oxide nanoring structure by introducing gold nanoparticles into the zinc oxide nanostructure. The method was found to complete the present application.

Thus, the present application, a method for manufacturing a hybrid zinc oxide nanoring structure in which a two-dimensional aligned ultra-high density zinc oxide nanoring structure and gold nanoparticles are introduced using a biblock copolymer having a self-assembly and a sol-gel process. To provide.

In addition, the present application is to provide a zinc oxide nanoring structure of the hybrid form in which the zinc oxide nanoring structure and gold nanoparticles are prepared by the above method.

In addition, the present disclosure is to provide a zinc oxide nanoring structure array in which the zinc oxide nanoring structure or a hybrid form of zinc oxide nanoring structure in which gold nanoparticles are introduced on a substrate.

However, the problem to be solved by the present application is not limited to the above-mentioned problem, and other problems not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above object, one aspect of the present invention, (a) dissolving a self-assembling diblock copolymer in a solvent to prepare a reverse micelle solution; (b) adding a solvent containing an alcohol and a zinc oxide precursor to prepare a zinc oxide sol-gel precursor solution; And (c) mixing the reverse micelle solution and the zinc oxide sol-gel precursor solution to prepare a reverse micelle solution containing a zinc oxide sol-gel precursor. To provide.

In one embodiment, the manufacturing method comprises the steps of: (d) coating a reverse micelle solution containing the zinc oxide sol-gel precursor on a substrate to produce a zinc oxide-self-assembled copolymer thin film; And (e) post-treating the thin film to remove the self-assembled copolymer: but may not be limited thereto.

In one embodiment, in step (b), the solvent containing the alcohol may further include a stabilizer, but is not limited thereto.

In one embodiment, in order to form a gold-zinc oxide nanoring structure of the hybrid form by introducing gold nanoparticles to the zinc oxide nanoring structure, in the step (d), the produced zinc oxide-self-assembled air It may further include, but is not limited to, immersing the coalescence thin film in an acidic aqueous solution containing a gold precursor.

Another aspect of the present application provides a gold-zinc oxide nanoring structure in a hybrid form by introducing gold nanoparticles into the zinc oxide nanoring structure or the zinc oxide nanoring structure prepared according to the method according to the above.

Another aspect of the present invention, by introducing gold nanoparticles to the zinc oxide nanoring structure or the zinc oxide nanoring structure prepared according to the above method, the gold-zinc oxide nanoring structure in a hybrid form is arranged on a substrate, A zinc oxide nanoring structure array is provided.

According to the present invention, by using a solvent containing a solvent or a stabilizer and an alcohol component and an alcohol component, the zinc oxide nanoring structure can be easily produced without a complicated multi-step manufacturing process for synthesizing conventional nanoring structures. The shape and arrangement of the zinc oxide nanoring structure can be controlled by varying the molecular weight of the self-assembled diblock copolymer or the relative volume fraction between the two blocks of the diblock copolymer and the concentration of the zinc oxide sol-gel precursor. The gold-zinc oxide nanoring structure in a hybrid form by introducing gold nanoparticles into the zinc oxide nanoring structure manufactured by the novel manufacturing method as described herein may be usefully used in various industrial fields requiring nanostructures. In addition, by introducing gold nanoparticles into the zinc oxide nanoring structure, it can be usefully used in various fields such as environmentally friendly devices, optical sensors and optical devices.

1 is a schematic diagram illustrating a process of manufacturing an ultra-high density zinc oxide nanoring structure array and a hybrid form of gold-zinc oxide nanoring structure array according to an embodiment of the present disclosure, wherein the chemical scheme is prepared by a zinc oxide sol-gel precursor. The reaction when

2 is an atomic force microscope (AFM) image in the process of manufacturing a zinc oxide nanoring structure according to an embodiment of the present application [(a) Step 1 of Example 1, (b) Step 4 of Example 1, (c) step 5 of example 1].

3 is a transmission electron microscope (TEM) image in the process of manufacturing a zinc oxide nanoring structure according to an embodiment of the present application [(a) An enlarged image of step 4, (b) (a) of Example 1 , (c) step 5 of example 1, (d) an enlarged image of (c)].

4 is an atomic force microscope (AFM) image of a process of separately introducing each component of a zinc oxide sol-gel precursor into a reverse micelle solution in which a self-assembled biblock copolymer according to an embodiment of the present invention is dissolved in a solvent [ Example 1 (a) step 1, (b) 2-propanol addition, (c) diethanolamine addition, (d) zinc acetate dihydrate addition, (e) zinc acetate dihydrate and 2-propanol addition, (f ) Zinc acetate dihydrate and diethanolamine addition, (g) zinc acetate dihydrate, 2-propanol and diethanolamine addition, (h) zinc acetate dihydrate, diethanolamine and 2-propanol addition].

5 is an atomic force microscope (AFM) image of a zinc oxide nanoring structure array prepared using self-assembled biblock copolymers having different molecular weights according to one embodiment of the present application [(a) Step of Example 1 5, (b) Step 5 of Example 3, (c) Step 5 of Example 4].

Figure 6 is an atomic force microscope (AFM) image of the zinc oxide nano ring structure array prepared by changing the relative concentration of the zinc oxide sol-gel precursor according to an embodiment of the present application [(a) Step 5 of Example 5, (b) step 5 of example 6, (c) step 5 of example 7, and (d) step 5 of example 8].

FIG. 7 is a graph showing an atomic force microscope (AFM) image and a pattern of an X-ray diffractometer (XRD) of a zinc oxide nanoring structure array prepared by heat treatment at a high temperature under an inert gas according to one embodiment of the present application [( a) an atomic force microscope (AFM) image of step 5 of example 2, (b) an X-ray diffractometer (XRD) pattern of step 5 of example 2].

8 is a field emission scanning electron microscope (FESEM) image and X-ray spectroscopy (EDS) analysis results of a hybrid gold-zinc oxide nanoring structure array in which gold nanoparticles are introduced according to an embodiment of the present disclosure [ (a) Field emission scanning electron microscope (FESEM) image of Example 9, (b) X-ray spectroscopy (EDS) results of Example 9].

Hereinafter, embodiments and examples of the present disclosure will be described in detail with reference to the accompanying drawings so that those skilled in the art may easily implement the present disclosure.

As those skilled in the art would realize, the described embodiments may be modified in various different ways, all without departing from the spirit or scope of the present invention. In the drawings, parts irrelevant to the description are omitted for simplicity of explanation, and like reference numerals designate like parts throughout the specification.

Throughout this specification, when a part is said to "include" a certain component, it means that it can further include other components, without excluding the other components unless specifically stated otherwise.

As used herein, the terms "about", "substantially", and the like, are used at, or in close proximity to, numerical values when manufacturing and material tolerances inherent in the meanings indicated are provided to aid the understanding herein. In order to prevent the unfair use of unscrupulous infringers. In addition, throughout this specification, "step to" or "step of" does not mean "step for."

One aspect of the present invention, (a) dissolving the self-assembly diblock copolymer in a solvent to prepare a reverse micelle solution; (b) adding a solvent containing an alcohol and a zinc oxide precursor to prepare a zinc oxide sol-gel precursor solution; And (c) mixing the reverse micelle solution and the zinc oxide sol-gel precursor solution to prepare a reverse micelle solution containing a sol-gel precursor. Provided is a method for manufacturing a zinc oxide nanoring structure. do.

In one embodiment of the present application, the method for producing a zinc oxide nanoring structure, (d) coating a reverse micelle solution containing a zinc oxide sol-gel precursor on a substrate to produce a zinc oxide-self-assembled copolymer thin film Doing; And (e) post-treating the thin film to remove the self-assembled copolymer: but may not be limited thereto.

In one embodiment, in step (b), the solvent containing the alcohol may further include a stabilizer, but is not limited thereto. For example, the stabilizer may be one selected from the group consisting of diethanolamine (DEA), monoethanolamine (MEA), and combinations thereof, but is not limited thereto.

In one embodiment, in order to form a gold-zinc oxide nanoring structure of the hybrid form by introducing gold nanoparticles to the zinc oxide nanoring structure, in the step (d), the produced zinc oxide-self-assembled air It may further include, but is not limited to, immersing the coalescence thin film in an acidic aqueous solution containing a gold precursor.

Hereinafter, a method of manufacturing a zinc oxide nanoring structure according to an embodiment of the present application will be described in detail with reference to the drawings, but the present application is not limited thereto.

First, step (a) according to the present invention is a step of preparing a reverse micelle solution by dissolving the self-assembling diblock copolymer in a solvent.

Amphiphilic diblock copolymer may be used as the self-assembled diblock copolymer, but is not limited thereto. The amphiphilic diblock copolymer is meant to include a hydrophilic block and a hydrophobic block. Dissolving only one block of the amphiphilic diblock copolymer in a selective solvent can form reverse micelles in solution. That is, the solvent may dissolve only a hydrophilic block or a hydrophobic block in the self-assembled double block copolymer in which the reverse micelle is formed. For example, the solvent may be selected from the group consisting of toluene, chloroform, tetrahydrofuran (THF), benzene, heptane, xylene, and combinations thereof, but is not limited thereto. The solvent may dissolve only hydrophobic blocks such as styrene blocks in the self-assembled double block copolymer in which the reverse micelles are formed.

As the diblock copolymer, for example, polystyrene-block-polyvinylpyridine may be used, and specifically, polystyrene-block-poly (4-vinylpyridine), polystyrene-block-poly (2-vinylpyridine), polystyrene -Block-polyethylene oxide (PS-b-PEO), polystyrene-block-polymethylmethacrylate (PS-b-PMMA), polyisoprene-block-poly (2-vinylpyridine) (PI-b-P2VP) , Poly (2-vinylpyridine) -block-polydimethylsiloxane (P2VP-b-PDMS) and the like may be used, and in particular, polystyrene-block-poly (4-vinylpyridine) may be used, but is not limited thereto. It doesn't happen.

In one embodiment, the shape and arrangement interval of the zinc oxide nanoring can be adjusted by controlling the molecular weight of the hydrophilic block and the hydrophobic block or the relative volume fraction of the two blocks of the amphiphilic copolymer, but is not limited thereto. For example, the molecular weight ratio of the hydrophilic block and the hydrophobic block may be adjusted to about 0.5: 1 to 7: 1 to adjust the shape and spacing of the zinc oxide nanorings.

Further, the reverse micelle solution of step (a) may contain 0.1 to 1.0 wt% of the self-assembled biblock copolymer, but is not limited thereto. If the self-assembled copolymer is less than 0.1% by weight, there may be a problem in that a uniform monomolecular film without defects may not be generated, and when the self-assembled copolymer is more than 1.0% by weight, a monomolecular film may not be produced. That is, in order to generate the reverse micelle monolayer, the conditions must be variably controlled by interlocking the solution concentration and the rotational speed during spin coating.

Next, step (b) is to prepare a zinc oxide sol-gel precursor solution containing an alcohol component.

The zinc oxide sol-gel solution of step (b) may be prepared by dissolving a zinc oxide precursor in a solvent containing an alcohol, or a mixed solution containing a solvent and a stabilizer containing alcohol, followed by stirring and aging. have.

As the solvent containing the alcohol, a solvent containing an alcohol selected from the group consisting of 2-propanol, ethanol, methanol, 2-methoxyethanol and combinations thereof may be used, but is not limited thereto. no.

As the zinc oxide precursor, zinc acetate dihydrate, zinc acetylacetonate monohydrate, zinc nitrate hexahydrate, and combinations thereof may be used, but is not limited thereto. no.

The stabilizer may increase the solubility of the zinc oxide precursor in the solvent containing the alcohol and induce chain rearrangement of the self-assembling diblock copolymer. Such stabilizers may include, but are not limited to, diethanolamine (DEA), monoethanolamine (MEA), and combinations thereof.

Step (b) is, for example, oxidized by adding a zinc oxide precursor to a solvent containing an alcohol at 50 to 80 ℃, or 60 to 70 ℃, or a mixed solution containing a solvent and a stabilizer containing alcohol Zinc sol-gel precursor solutions can be prepared.

The mixing ratio of the zinc oxide precursor and the stabilizer may be maintained at 1: 0.1 to 2, for example, and the concentration of the zinc oxide sol-gel precursor may be, for example, 0.3 M to 2.0 M. However, it is not limited thereto.

Next, step (c) is a step of mixing and stirring the reverse micelle solution prepared in step (a) and the sol-gel precursor solution prepared in step (b).

The alcohol component of the sol-gel precursor prepared in step (b) rearranges hydrophilic block chains, such as, for example, P4VP blocks, in the copolymer of step (a) to open reverse micelles, and simultaneously zinc acetate Zinc oxide precursors such as dihydrate can be bound to hydrophilic moieties such as the open P4VP block (see Experimental Example 1).

Next, step (d) is to prepare a zinc oxide-self-assembled copolymer thin film by spin coating a reverse micelle solution containing the zinc oxide sol-gel precursor mixed in step (c) on a substrate. .

The substrate herein may be a silicon wafer, quartz, glass, mica substrate, or a combination thereof, but is not limited thereto.

Next, step (e) is to prepare a zinc oxide nanoring structure by post-treating the thin film prepared in step (d) to remove the self-assembly copolymer. The post-treatment process may remove the copolymer and oxidize the zinc oxide precursor.

The post-treatment may be performed through a process including oxygen plasma exposure, heat treatment, or ultraviolet irradiation, and more specifically, oxygen plasma exposure or heat treatment. For example, the post-treatment may be performed by exposure to 100 W of oxygen plasma for 30 seconds or by heat treatment at 400 to 800 ° C., more specifically at a high temperature of 400 to 600 ° C., under an inert gas atmosphere for 1 hour. It may include, but is not limited to, removing the coarse copolymer.

The present application provides a zinc oxide nanoring structure manufactured by the method, and in one embodiment, the zinc oxide nanoring structure has an average center-to-center distance between the nanorings between 50 nm and 100 nm and hexagonal butt. It may have a wurtzite crystal structure, but is not limited thereto.

In one embodiment, the gold-zinc oxide nanoring in a hybrid form may be prepared by introducing gold nanoparticles into the zinc oxide nanoring structure prepared according to the present application (see Experimental Example 5).

Specifically, the zinc oxide-self-assembled copolymer thin film prepared in step (d) is immersed in an acidic aqueous solution containing a precursor of gold nanoparticles to introduce gold nanoparticles into the zinc oxide nanoring structure. The gold nanoparticle precursor may include, for example, HAuCl ₄ , KAuCl ₄ , NaAuCl ₄ , NH ₄ AuCl ₄ , LiAuCl ₄ , KAuBr ₄ , NaAuBr ₄ , HAuBr ₄ , or a combination thereof. The acidic aqueous solution may include, for example, hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, or a combination thereof.

Subsequently, the zinc oxide nanoring structure into which the gold nanoparticles prepared according to the present application are introduced is subjected to plasma treatment to remove the diblock copolymer template, and to oxidize and reduce the zinc oxide precursor and the gold nanoparticle precursor, respectively. Hybrid zinc oxide nanorings into which gold nanoparticles are introduced can be prepared (see FIG. 8 for the manufactured zinc oxide nanorings).

In addition, the present application provides a zinc oxide nanoring structure prepared by the above method and a zinc oxide nanoring structure in a hybrid form in which gold nanoparticles are introduced.

In addition, the present application provides a zinc oxide nanoring structure array in which the zinc oxide nanoring structure or a hybrid type zinc oxide nanoring structure in which gold nanoparticles are introduced on a substrate is arranged.

The zinc oxide nanoring structure arrangement prepared according to the present invention can easily control the shape and arrangement of the zinc oxide nanoring by changing the molecular weight of the diblock copolymer or the relative volume fraction between the two blocks.

Looking at the results of observing the structural change of the nanostructures by varying the molecular weight or relative volume fraction of the diblock copolymer with respect to the zinc oxide nanoring structure prepared according to the present application, the shape and arrangement of the zinc oxide nanorings according to the changed conditions It can be seen that can control (see Experimental Example 2).

Specifically, the zinc oxide nanoring structure prepared according to the present invention is removed by the plasma treatment of the diblock copolymer template and the zinc oxide precursor is oxidized, and the interval between the zinc oxide nanorings according to the molecular weight of the diblock copolymer is clear. The difference is shown (see FIG. 5).

In addition, the zinc oxide nanoring structure prepared according to the present application can easily control the shape of the zinc oxide nanoring by changing the concentration of the zinc oxide sol-gel precursor.

According to the results of observing the structural change of the nanostructures by varying the concentration of the zinc oxide sol-gel precursor in the zinc oxide nanoring spherical body prepared according to the present application, the shape of the zinc oxide nanoring structure was controlled according to the changed conditions. It can be seen that (see Experimental Example 3).

Specifically, when the zinc oxide nanoring structure prepared according to the present application is plasma treated to remove the diblock copolymer template, and the zinc oxide precursor is oxidized, the form of the zinc oxide nanoring depends on the concentration of the zinc oxide sol-gel precursor. A distinct difference appears (see FIG. 6).

Therefore, the zinc oxide nanoring structure of the present application can control the shape and arrangement interval of the zinc oxide nanoring by using a biblock copolymer having different molecular weights, and also change the concentration of the zinc oxide sol-gel precursor. You can control the shape of the nanoring.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely to illustrate the present application, the content of the present application is not limited by the following examples.

EXAMPLE

Example 1 Preparation of Zinc Oxide Nanoring Structures 1

Step 1: preparing reverse micelle solution containing self-assembled copolymer

Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, M _n ^ps = 41.5 kg / mol, M _n ^p4vp = 17.5 kg / mol, M _w / M _n = 1.07) was dissolved in toluene at a concentration of 0.5% by weight to prepare a reverse micelle solution.

Step 2: Preparation of Sol-Gel Precursor Solution

A zinc oxide sol-gel precursor solution was prepared by adding zinc acetate dihydrate, a zinc oxide precursor, to a mixed solution of 2-propanol, a solvent, and diethanolamine, or DEA, as a stabilizer. It was. The molar ratio of zinc acetate dihydrate and diethanolamine was 1: 1, and the concentration of the zinc acetate solution was 0.5 M. The zinc oxide sol-gel precursor solution was stirred at 65 ° C. for 1 hour to prepare a sol-gel precursor solution.

Step 3: Preparation of reverse micelle solution containing zinc oxide sol-gel precursor

The diblock copolymer reverse micelle containing the zinc oxide sol-gel precursor was added to the reverse micelle solution of step 1 by adding 1 vol% of the sol-gel precursor solution of step 2, followed by stirring at room temperature for 1 day. Prepared.

Step 4: Zinc Oxide-Self Assembly Copolymer Thin Film Preparation

A zinc oxide-self-assembled copolymer thin film was prepared by spin coating the reverse micelle solution containing the zinc oxide sol-gel precursor prepared in step 3 at 2000 rpm for 60 seconds.

Step 5: Removal of Self-Assembly Copolymers by Post Treatment

A zinc oxide nanoring structure was prepared by exposing 100 W of oxygen plasma to the zinc oxide-self-assembled copolymer thin film of step 4 for 30 seconds to remove the diblock copolymer and oxidizing the zinc oxide precursor.

Example 2 Preparation of Zinc Oxide Nanoring Structure 2

Except that the step 1 of Example 1 was removed by heat treatment for 1 hour at a temperature of 400 ℃ or 600 ℃ under an inert gas atmosphere was prepared in the same manner as in Example 1.

Example 3 Preparation of Zinc Oxide Nanoring Structures 3

Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, M _n ^ps = 122 kg / mol, M _n in step 1 of Example 1 ^p4vp = 22 kg / mol, M _w / M _n = 1.15) was prepared in the same manner as in Example 1 except that the reverse micelle solution was prepared by dissolving ^{towluene at} a concentration of 0.5% by weight.

Example 4 Fabrication of Zinc Oxide Nanoring Structures 4

Polystyrene-block-poly (4-vinyl pyridine), PS-b-P4VP, M _n ^ps = 22 kg / mol, M _n in step 1 of Example 1 ^p4vp = 22 kg / mol, M _w / M _n = 1.09) was prepared in the same manner as in Example 1 except that the reverse micelle solution was prepared by dissolving ^{towene in} a concentration of 0.5% by weight.

Example 5 Fabrication of Zinc Oxide Nanoring Structures 5

Example 1 was prepared in the same manner as in Example 1, except that the concentration of the zinc acetate solution of 0.3 M in step 2 of.

Example 6 Fabrication of Zinc Oxide Nanoring Structures 6

Example 1 was prepared in the same manner as in Example 1, except that the concentration of the zinc acetate solution in step 2 of 0.7 M.

Example 7 Fabrication of Zinc Oxide Nanoring Structures 7

Example 1 was prepared in the same manner as in Example 1, except that the concentration of the zinc acetate solution was prepared in 1.0 M in step 2.

Example 8 Fabrication of Zinc Oxide Nanoring Structures 8

Example 1 was prepared in the same manner as in Example 1, except that the concentration of the zinc acetate solution in step 2 of 2.0 M.

Example 9 Fabrication of Hybrid Gold-Zinc Oxide Nanoring Structures

The zinc oxide-self-assembled copolymer thin film of Step 4 of Example 1 was immersed in an acidic aqueous solution containing gold nanoparticle precursors for 3 hours to introduce gold nanoparticle precursors, and 100 W of oxygen plasma for 30 seconds. The diblock copolymer was removed by exposure and the zinc oxide precursor was oxidized to prepare a hybrid gold-zinc oxide nanoring structure.

Experimental Example 1 Formation of Nano Ring Structure by Alcohol Component

The following experiment was carried out to reveal that the reverse micelle of the diblock copolymer is reconstituted by the alcohol component.

In Example 1, the surface of the thin film was observed with an atomic force microscope (AFM) and a transmission electron microscope (TEM), and is shown in FIGS. 2 and 3, respectively.

For Example 1, the surface was observed before and after the addition of the zinc oxide precursor and after the oxygen plasma was observed by atomic force microscopy (AFM) and transmission electron microscope (TEM), respectively. More specifically, the surface of the thin film obtained by spin coating the solution of Step 1 of Example 1 was observed with an atomic force microscope (AFM), and is shown in FIG. 2 (a), and the step 4 of Example 1 The surface was observed with an atomic force microscope (AFM) and a transmission electron microscope (TEM), and is shown in FIGS. 2B and 3A and 3B, respectively, and the surface of step 5 of Example 1 was shown. Observed by an atomic force microscope (AFM) and transmission electron microscope (TEM) and shown in Figure 2 (c) and 3 (c) and (d), respectively. 3B and 3D are enlarged images.

As can be seen in FIG. 2 (a), polystyrene-block-poly (4-vinylpyridine) reverse micelles in a regularly ordered arrangement could be observed. Also, as can be seen in FIGS. 2 (b) and 3 (a) and 3 (b), nanopores well aligned in zinc oxide-self-assembled copolymer thin films containing zinc oxide sol-gel precursors It could be observed. The alcohol component contained in the zinc oxide sol-gel precursor and the diethanolamine component used in Example 1 are induced by reconstructing the 4-vinylbiridine block to open reverse micelles, thereby forming nanopores. Could confirm. Furthermore, as can be seen in FIGS. 2 (c) and 3 (c) and (d), the zinc oxide nanoring structure can be obtained by treating the zinc oxide-self-assembled copolymer thin film with oxygen plasma. It was confirmed that the plasma treatment removed the polymer template and oxidized the zinc oxide precursor.

Particularly, in order to confirm that the reconstitution of reverse micelles was influenced by diethanolamine, the surface of the thin film represented by separate introduction of each component of the zinc oxide sol-gel precursor was observed by atomic force microscope (AFM). 4 is shown. More specifically, the surface of the thin film obtained by spin coating the solution of Step 1 of Example 1 was observed in an atomic force microscope (AFM) and is shown in FIG. 4 (a), and the solution of Step 1 of Example 1 The surface of the thin film obtained by spin coating the mixed solution after 2-propanol, diethanolamine, and zinc acetate dihydrate was added thereto was observed by atomic force microscope (AFM), and FIGS. It is shown to (d), respectively. In addition, the following experiment was performed to observe the structural change caused by the mixing procedure of 2-propanol and diethanolamine in the mixed solution of zinc acetate dihydrate added to the solution of Step 1 of Example 1, The surface of the thin film was observed with an atomic force microscope (AFM) and is shown in FIGS. 4E, 4F, 7G and 4H.

As can be seen in Figure 4, when the diethanolamine of the zinc oxide precursor component is added, it was confirmed that the opening of the polystyrene-block-poly (4-vinylpyridine) reverse micelles was induced regardless of the mixing order.

Experimental Example 2 Structural Changes of Zinc Oxide Nanoring Structures According to Molecular Weight or Relative Volume Fraction

The following experiment was conducted to investigate the structural change of the zinc oxide nanoring structure according to the change in molecular weight or relative volume fraction of the diblock copolymer.

For Examples 1, 3, and 4, the surface of each thin film was observed with an atomic force microscope (AFM), and is shown in FIG. 5. More specifically, the surface of step 5 of Examples 1, 3, and 4 was observed with an atomic force microscope (AFM), and shown in FIGS. 5A, 5B, and 5C, respectively. In addition, the surface of each thin film was magnified and observed with an atomic force microscope (AFM) to be inserted in FIG. 5, and a cross-section profile was obtained from the enlarged image and inserted into the bottom of FIG. 5.

As can be seen in FIG. 5 (a), which is an atomic force microscope (AFM) image of the zinc oxide nanoring prepared in Example 1, the uniform distribution and packing density of the quasi-hexagonal array are shown. Eggplants were able to obtain a zinc oxide nanoring structure, and the average center-center distance between the nanorings was about 73 nm.

As can be seen in (b) of FIG. 5, which is an atomic microscope image of the zinc oxide nanoring prepared in Example 3, the distance between the centers of the zinc oxide nanorings due to the relatively high molecular weight of the zinc oxide nanorings was found in Example 1 The increase was further observed when compared with the distance between the centers of the zinc oxide nanorings prepared in.

As can be seen in (c) of FIG. 5, which is an atomic microscope image of the zinc oxide nanoring prepared in Example 4, the zinc oxide nanoring prepared in Examples 1 and 3 has a packing density of the zinc oxide nanoring. It was observed that the packing density was larger than, and the distance between the centers was reduced to about 57 nm. It was also observed that the shape of the zinc oxide nanostructures is closer to the shape of a disk with a groove in the center than the ring.

As can be seen in Figure 5, using a diblock copolymer having a different molecular weight, polystyrene-block-poly (4-vinylpyridine), it is confirmed that the distance between the center and the shape of the zinc oxide nanoring is distinctly different Through this, it was confirmed that the shape and spacing interval of each zinc oxide nanoring can be adjusted according to the molecular weight of the diblock copolymer or the change of the relative volume fraction between the two blocks.

Experimental Example 3 Structural Changes of Zinc Oxide Nano Ring Structures According to Concentration of Zinc Oxide Sol-Gel Precursor

The following experiment was conducted to investigate the structural change of the zinc oxide nanoring structure according to the concentration change of the zinc oxide sol-gel precursor.

For Examples 1, 5, 6, 7, and 8, the surface of each thin film was observed with an atomic force microscope (AFM) and shown in FIGS. 2 and 6. In more detail, the surface of step 5 of Examples 1, 5, 6, 7 and 8 was observed with an atomic force microscope (AFM), and FIGS. 2 (c) and 6 (a), 6 (b), It is shown to (c) and (d).

As can be seen in (c) of FIG. 2, which is an atomic force microscope (AFM) image of the zinc oxide nanoring prepared in Example 1, zinc oxide nano having a uniform distribution and a packing density of a quasi-hexagonal array The ring structure was obtained.

As can be seen in Figure 6 (a) and (b) of the atomic force microscope (AFM) image of the zinc oxide nanoring prepared in Examples 5 and 6, the shape and distribution of the zinc oxide nanoring It can be observed that similar to the nanoring structure of zinc oxide prepared in Example 1.

As can be seen in Figure 6 (c) and (d) of the atomic force microscope (AFM) image of the zinc oxide nanoring prepared in Examples 7 and 8, the shape of the zinc oxide nanoring is distorted, It was observed that the overlap between the adjacent nano-rings, especially in the case of the zinc oxide structure prepared in Example 8 was confirmed that the elliptical and elongated nano-rings are mainly obtained.

As can be seen in Figures 2 and 6, when a relatively large amount of zinc oxide precursor is introduced, that is, when the concentration of the zinc oxide sol-gel precursor is increased, the shape of the zinc oxide nanoring changes as a result. Through this, it was found that the amount of precursor that poly (4-vinylpyridine) can accommodate is limited to 0.5 M in order to obtain a zinc oxide nanoring structure having uniform distribution and quasi-hexagonal packing density. .

From this, it can be seen that the phenomenon in which the ultra-high density zinc oxide nanoring structure arrangement of the present application plays a large role of the alcohol component contained in the zinc oxide precursor, and uses a diblock copolymer having a different composition or It was found that the shape and arrangement of the zinc oxide nanoring structure could be controlled by changing the relative concentrations.

Experimental Example 4 Crystal Structure of Zinc Oxide Nano Ring Structure

In order to investigate the crystal structure of the zinc oxide nanoring structure, the following experiment was performed.

The nanoring structures of Example 2 were analyzed by atomic force microscope (AFM) and X-ray diffractometer (XRD), and are shown in FIG. 7. More specifically, the surface of step 5 of Example 2 was observed in an atomic force microscope (AFM), and is shown in FIG. 7 (a). It is shown in Figure 7 (b).

As can be seen in Figure 7, after the heat treatment at a high temperature in an inert gas atmosphere, it was possible to obtain the arrangement and crystal structure of the zinc oxide nanoring structure. From the atomic force microscope (AFM) image, it was found that the heat-treated at high temperature under an inert gas atmosphere can obtain an array of oxidized zinc oxide nanoring herbicides while removing the self-assembled copolymer. From the specific peak of the X-ray diffractometer (XRD), it can be seen that the zinc oxide nanoring structure prepared in Example 2 has a hexagonal wurtzite structure. In addition, as can be seen in Figure 7 (b), the higher the heat treatment temperature was confirmed that the peak intensity of the X-ray diffractometer (XRD) increased, from which the zinc oxide nanoring structure with increased crystallinity Could be manufactured.

Experimental Example 5 Hybridization of Zinc Oxide Nano Rings by Introduction of Gold Nanoparticles

In order to identify the hybrid gold-zinc oxide nanoring structure formed by introducing gold nanoparticles, the following experiment was performed.

In Example 9, the surface of the hybrid thin film was observed by field emission scanning electron microscopy (FESEM), and is shown in FIG. 8 (a). The gold and zinc oxide components were analyzed by X-ray spectroscopy (EDS). It is shown to 8 (b).

As can be seen in FIG. 8, it was confirmed that the gold nanoparticles were successfully hybridized with the zinc oxide nanorings. Field emission injection that the gold nanoparticles hybridized with the zinc oxide nanoring after the diblock copolymer was removed by selectively binding the negatively charged gold nanoparticle precursors dissociated in an acidic aqueous solution to protonated poly (4-vinylpyridine). It was confirmed from an electron emission microscope (SEM). In addition, the introduction of gold nanoparticles was confirmed through X-ray spectroscopy (EDS) of the hybrid thin film.

Claims (20)

1. (a) dissolving the self-assembling diblock copolymer in a solvent to prepare a reverse micelle solution;

   (b) adding a solvent containing an alcohol and a zinc oxide precursor to prepare a zinc oxide sol-gel precursor solution; And

   (c) mixing the reverse micelle solution and the zinc oxide sol-gel precursor solution to prepare a reverse micelle solution containing a zinc oxide sol-gel precursor;

   A method of manufacturing a zinc oxide nanoring structure, comprising a.
2. The method of claim 1,

   (d) coating a reverse micelle solution containing the zinc oxide sol-gel precursor onto a substrate to prepare a zinc oxide-self-assembled copolymer thin film; And,

   (e) post-treating the thin film to remove the self-assembling diblock copolymer: further comprising, zinc oxide nanoring structure manufacturing method.
3. The method of claim 1,

   The alcohol comprises a one selected from the group consisting of propanol, ethanol, methanol, 2-methoxyethanol, and combinations thereof.
4. The method of claim 1,

   In the step (b), the solvent containing the alcohol further comprises a stabilizer, the method of producing a zinc oxide nanoring structure.
5. The method of claim 4, wherein

   The stabilizer is selected from the group consisting of diethanolamine (diethanolamine, DEA), monoethanolamine (MEA), and combinations thereof, The method of producing a zinc oxide nanoring structure.
6. The method of claim 1,

   The self-assembling diblock copolymer will include an amphiphilic diblock copolymer, a method of producing a zinc oxide nanoring structure.
7. The method of claim 6,

   The amphiphilic diblock copolymers are polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), polystyrene-block- Polyethylene oxide (PS-b-PEO), polystyrene-block-polymethylmethacrylate (PS-b-PMMA), polyisoprene-block-poly (2-vinylpyridine) (PI-b-P2VP), poly ( 2-vinylpyridine) -block-polydimethylsiloxane (P2VP-b-PDMS) and a combination thereof, the method of manufacturing a zinc oxide nanoring structure.
8. The method of claim 1,

   In the step (a), the solvent is to selectively dissolve only one block of the diblock contained in the self-assembled double block copolymer, zinc oxide nano ring structure manufacturing method.
9. The method of claim 8,

   Wherein the solvent comprises one selected from the group consisting of toluene, chloroform, tetrahydrofuran (THF), benzene, heptane, xylene, and combinations thereof.
10. The method of claim 1,

    The reverse micelle solution of step (a) will contain 0.1 wt% to 1.0 wt% of the self-assembling diblock copolymer.
11. The method of claim 1,

    And the zinc oxide precursor is selected from the group consisting of zinc acetate dihydrate, zinc acetylacetonate monohydrate, zinc nitrate hexahydrate, and combinations thereof.
12. The method of claim 4, wherein

    The molar ratio of the zinc oxide precursor and the stabilizer is 1: 0.1 to 2, the method of manufacturing a zinc oxide nanoring structure.
13. The method of claim 1,

    In the step (b), the concentration of the zinc oxide sol-gel precursor is 0.3 M to 2 M, the manufacturing method of the nano-ring structure.
14. The method of claim 2,

    And the substrate is selected from the group consisting of silicon wafers, quartz, glass mica, and combinations thereof.
15. The method of claim 2,

    The post-treatment will include a process selected from the group consisting of oxygen plasma treatment, heat treatment, ultraviolet irradiation, and combinations thereof.
16. The method of claim 2,

    In order to form a gold-zinc oxide nanoring structure in a hybrid form by introducing gold nanoparticles into the zinc oxide nanoring structure, in the step (d), the prepared zinc oxide-self-assembled copolymer thin film to a gold precursor Further comprising the step of immersing in an acidic aqueous solution containing, a method for producing a zinc oxide nanoring structure.
17. The method of claim 16,

    The precursor of the gold nanoparticles are oxidized, including those selected from the group consisting of HAuCl ₄ , KAuCl ₄ , NaAuCl ₄ , NH ₄ AuCl ₄ , LiAuCl ₄ , KAuBr ₄ , NaAuBr ₄ , HAuBr ₄ , and combinations thereof. Method of manufacturing zinc nanoring structure.
18. The method of claim 16,

    The acidic aqueous solution comprises an acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, acetic acid, formic acid, and combinations thereof, a method for producing a zinc oxide nanoring structure.
19. Zinc oxide nanoring structure produced by the method of any one of claims 1 to 18.
20. An array of zinc oxide nanoring structures, wherein the zinc oxide nanoring structures according to claim 19 are arranged on a substrate.

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