KR101335616B1 - PRODUCING METHOD OF Au NANOPARTICLE PATTERN HAVING LOCALIZED SURFACE PLASMON RESONANCE COUPLING PROPERTY, AND Au NANOPARTICLE PATTERN BY THE SAME - Google Patents

Abstract

The present application is a manufacturing method that can control the pattern of gold nanoparticles exhibiting a specific surface plasmon resonance coupling phenomenon, the gold nanoparticle pattern prepared according to this, a nanostructure comprising the gold nanoparticle pattern, and a sensor comprising the nanostructure It is about.

Description

FIELD OF THE INVENTION A method for producing a gold nanoparticle pattern having a localized surface plasmon resonance coupling phenomenon and a gold nanoparticle pattern thereby

The present application is a manufacturing method that can control the pattern of gold nanoparticles exhibiting a specific surface plasmon resonance coupling phenomenon, the gold nanoparticle pattern prepared according to this, a nanostructure comprising the gold nanoparticle pattern, and a sensor comprising the nanostructure It is about.

Recently, self-assembly technology has been 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 a form in which two or more polymer chains are 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, spontaneous or cylindrical micelles of spherical, cylindrical, or the like can be spontaneously formed.

Dissolving the diblock copolymer in a solvent selective to only one block can form micelles or reverse micelles in solution. At this time, the solvent is a non-polar solvent, the form of the hydrophilic block is located outside the micelle, the solvent is a polar solvent, the form of the hydrophilic block is located inside the reverse micelles. When the micelle or reverse micelle thin film coated on the solid substrate is immersed in a solvent selective to the inner block, the process of moving and exposing to the surface by rearrangement of the inner block polymer chain is defined as the reconstruction phenomenon of the micelle or reverse micelle. . Nanopores (nano ring shape) can be observed by reconstitution of spherical micelles or reverse micelles.

In addition, when the self-assembled biblock copolymer is used as a template, an array of various inorganic materials such as various semiconductor oxides or metal nanoparticles can be easily manufactured, and the size of the particles is within the nanostructure of the diblock copolymer. It can be limited to nanometer size without additional treatment, and the arrangement of the particles is also limited by the size and spacing of the nanostructures to control the size and arrangement of the particles.

Nanosized gold particles exhibit unusual localized surface plasmon resonance (LSPR) properties. This phenomenon is affected by the size of the gold nanoparticles, the distance between neighboring nanoparticles, and the surrounding environment of the gold nanoparticles, such that the movement of the characteristic peaks or the increase in absorbance are exhibited. The unusual optical properties of these gold nanoparticles are of increasing interest due to potential applications such as optical devices and optical sensors.

For example, regularly ordered gold nanoparticles can observe an increase in the field due to plasmon coupling between gold nanoparticles in addition to local surface plasmon resonance of individual gold nanoparticles, which is a protein It can be effectively applied to sensing DNA. Conversely, if the arrangement of gold nanoparticles is not regular and the nanoparticles form clusters with each other, the plasmon bonds between the gold nanoparticles are strongly induced, so that the wavelengths of characteristic peaks, such as one-dimensional nanomaterials, are strong. The change can be observed, which induces a change in the emission color, and thus is applicable to an optical display element.

Korean Patent Laid-Open Publication No. 10-2010-0069105 discloses a process of forming a micelle by self-assembly by mixing a nanoparticle including an organic ligand and a block copolymer including a block repeating unit having different solubility parameters in a solvent. A method for producing a nanoparticle / block copolymer is disclosed.

Accordingly, the present application is a method for producing a gold nanoparticle pattern capable of controlling a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance coupling phenomenon, a nanostructure comprising a gold nanoparticle pattern prepared by the above method, and the nanostructure To provide a sensor comprising a.

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.

The method for preparing a gold nanoparticle pattern according to the first aspect of the present disclosure may include the following:

(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution; (b) coating the reverse micelle solution on a solid substrate to prepare a self-assembled biblock copolymer reverse micelle thin film; (c) inducing a reconstruction of the reverse micelle thin film; And (d) adsorbing gold nanoparticles stabilized by citrate ligand on the reconstituted reverse micelle thin film.

The method for preparing a gold nanoparticle pattern according to the second aspect of the present disclosure may include the following:

(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution; (b) coating the reverse micelle solution on a solid substrate to prepare a self-assembled biblock copolymer reverse micelle thin film; And (c ′) adsorbing gold nanoparticles stabilized by citrate ligand while inducing reconstitution of the reverse micelle thin film.

A third aspect of the present application provides a nanostructure prepared by the method according to the first aspect or the second aspect and comprising a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon.

The fourth aspect of the present application provides a sensor including the nanostructure.

According to the present invention, the pattern of the gold nanoparticles can be prepared by reconstitution of the self-assembled biblock copolymer reverse micelle, and by controlling the molecular weight of the self-assembled copolymer, the size of the gold nanoparticles and the degree of deposition of the gold nanoparticles, etc. It is possible to control the shape and arrangement of the gold nanoparticle pattern, and to control local surface plasmon resonance coupling accordingly, which can be used for sensing various materials, and industries requiring nanostructures including such nanoparticle patterns. It can be usefully used in the field.

1 is a schematic diagram illustrating a process of preparing a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon according to an embodiment of the present application.
2 (a) and 2 (b) are atomic force microscope (AFM) images in the process of manufacturing a gold nanoparticle pattern according to an embodiment of the present application {FIG. 2 (a): Step of Example 1 ( b), FIG. 2 (b): Step (c) of Example 1}.
3 (a) to 3 (g) are field emission scanning electron microscopy (FESEM) images of a gold nanoparticle pattern prepared by a type I method according to one embodiment of the present application {FIG. 3 (a): Example Step (d) of Figure 1, Figure 3 (b): Step (d) of Embodiment 2, Figure 3 (c): Step (d) of Figure 3, Figure 3 (d): Step (d) of Embodiment 4 3 (e): Step (d) of Example 5, FIG. 3 (f): Step (d) of Example 6, FIG. 3 (g): Step (d) of Example 7.}.
4 is an ultraviolet visible spectrophotometer graph of a pattern of gold nanoparticles prepared by a type I method according to one embodiment of the present disclosure.
5 (a) to 5 (e) are field emission scanning electron microscope (FESEM) images of gold nanoparticle patterns prepared by the Type II method according to an embodiment of the present application (FIG. 5 (a) Example 8 Step (c '), FIG. 5 (b) Step 9 (c') of the ninth embodiment, FIG. 5 (c) Step (c ') of the tenth embodiment, FIG. 5 (e) step (c ') of Example 12}.
FIG. 6 is an ultraviolet visible spectrophotometer graph of a pattern of gold nanoparticles prepared by a Type II method according to one embodiment of the present disclosure.
FIG. 7 is a graph of surface sensitized Raman scattering of para-aminothiophenol adsorbed on a gold nanoparticle pattern prepared by a type I method according to one embodiment of the present disclosure.
FIG. 8 is a graph of surface sensitized Raman scattering of para-aminothiophenol adsorbed onto a gold nanoparticle pattern prepared by a Type II method according to one embodiment of the present disclosure.
9 is a schematic diagram of preparing a gold nanoparticle array from a self-assembled copolymer template according to one embodiment of the present disclosure.
FIG. 10 is an ultraviolet-visible spectrophotometer graph for evaluating sensing ability to use a gold nanoparticle array prepared from a self-assembled copolymer template according to an embodiment of the present disclosure as a sensor for detecting protein.

Hereinafter, embodiments and examples 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.

It should be understood, however, that the present invention may be embodied in many different forms and is not limited to the embodiments and examples described herein. In the drawings, the same reference numbers are used throughout the specification to refer to the same or like parts.

Throughout this specification, when a part is referred to as being "connected" to another part, it is not limited to a case where it is "directly connected" but also includes the case where it is "electrically connected" do.

Throughout this specification, when a member is located "on" another member, this includes not only when one member is in contact with another member but also when another member exists between the two members.

Throughout this specification, when an element is referred to as "including " an element, it is understood that the element may include other elements as well, without departing from the other elements unless specifically stated otherwise.

The terms "about "," substantially ", etc. used to the extent that they are used throughout the specification are intended to be taken to mean the approximation of the manufacturing and material tolerances inherent in the stated sense, Accurate or absolute numbers are used to help prevent unauthorized exploitation by unauthorized intruders of the referenced disclosure. The word " step (or step) "or" step "used to the extent that it is used throughout the specification does not mean" step for.

Throughout this specification, the term "combination of these" included in the expression of the mark of the form refers to one or more mixtures or combinations selected from the group consisting of the elements described in the mark of the form of Markus, wherein the component It means to include one or more selected from the group consisting of.

The present application is a polystyrene-block-poly (vinyl pyridine) having self-assembly properties of the reverse micelles and control and preparation of gold nanoparticle pattern by selective adsorption of gold nanoparticles It provides a method, a nanostructure comprising the gold nanoparticle pattern, and a sensor comprising the nanostructure.

Method for producing a gold nanoparticle pattern according to the first aspect of the present application (two-step method, hereinafter referred to as "type I method"), (a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution step; (b) coating the reverse micelle solution on a solid substrate to prepare a self-assembled biblock copolymer reverse micelle thin film; (c) inducing reconstitution of the reverse micelle thin film; And (d) adsorbing gold nanoparticles stabilized by citrate ligand on the reconstituted reverse micelle thin film.

The method for producing a gold nanoparticle pattern according to the second aspect of the present application (a one-step method, hereinafter referred to as “type II method”) is a method for preparing a reverse micelle solution by dissolving a self-assembled diblock copolymer in a solvent. step; (b) coating the reverse micelle solution on a solid substrate to prepare a self-assembled biblock copolymer reverse micelle thin film; And (c ′) inducing reconstitution of the reverse micelle thin film and simultaneously adsorbing gold nanoparticles stabilized by citrate ligand.

In one embodiment of the present application, the self-assembled diblock copolymer may include an amphiphilic diblock copolymer, but is not limited thereto.

In one embodiment of the invention, the amphiphilic diblock copolymer is polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b -P2VP), polystyrene-block-poly (ethylene oxide) (PS-b-PEO), polystyrene-block-poly (acrylic acid) (PS-b-PAA), and combinations thereof It may be, but is not limited thereto.

In one embodiment of the present application, the solvent may be to selectively dissolve only one block of the self-assembled biblock copolymer, but is not limited thereto.

In one embodiment of the present application, the solvent may be one selected from the group consisting of chloroform, tetrahydrofuran (THF), toluene, and combinations thereof, but is not limited thereto.

In one embodiment of the present application, the reverse micelle solution may contain about 0.1 wt% to about 1.0 wt% of the self-assembled diblock copolymer, but is not limited thereto.

In one embodiment of the present application, the solid substrate may be a silicon wafer, but is not limited thereto.

In one embodiment of the present application, the reconstitution of the reverse micelle thin film may be induced by immersing in a solvent for selectively dissolving only one block of the self-assembled biblock copolymer, but is not limited thereto.

In one embodiment of the present application, the solvent may be selected from the group consisting of alcohol, water, acidic solutions, and combinations thereof, but is not limited thereto.

In one embodiment of the present application, the immersion time may be about 10 minutes to about 24 hours, but is not limited thereto.

In one embodiment of the present application, the gold nanoparticles may include gold nanoparticles modified by a negatively charged molecule, but is not limited thereto.

The third aspect of the present application provides a nanostructure prepared according to the method of the first side or the second side and comprising a gold nanoparticle pattern exhibiting a unique local surface plasmon resonance binding phenomenon.

The fourth aspect of the present application provides a sensor including the nanostructure.

Hereinafter, a method of manufacturing a gold nanoparticle pattern according to an embodiment of the present application will be described with reference to FIG. 1.

First, a method of manufacturing a gold nanoparticle pattern according to the type I method will be described.

(a) The self-assembled copolymer was dissolved in a solvent to prepare a reverse micelle solution.

The self-assembled copolymer is an amphiphilic diblock copolymer, which can form reverse micelles in a solution when dissolved in a solvent selective to only one block. As the diblock copolymer, for example, polystyrene-block-polyvinylpyridine can be used, for example, polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), polystyrene-block-poly (ethylene oxide) (PS-b-PEO), polystyrene-block-poly (acrylic acid) (PS-b-PAA), and these It can be used selected from the group consisting of combinations, for example, polystyrene-block-poly (4-vinylpyridine) and polystyrene-block-poly (2-vinylpyridine) can be used, polystyrene-block-poly More preferred is (4-vinylpyridine), but is not limited thereto. As the solvent, a solvent having a selective affinity for the styrene block in the diblock copolymer may be used. For example, toluene, chloroform, tetrahydrofuran (THF), etc. may be used, and among them, toluene may be used. desirable.

The reverse micelle solution may contain, for example, about 0.1 wt% to about 1.0 wt% of the self-assembled copolymer, but is not limited thereto. If the self-assembled copolymer is less than about 0.1% by weight, there is a problem in that a uniform monomolecular film without defects is not produced, and when the self-assembled copolymer is more than about 1.0% by weight, a monomolecular film is not produced. The reverse micelle solution may comprise, for example, about 0.1 wt% to about 1.0 wt%, about 0.2 wt% to about 0.9 wt%, about 0.3 wt% to about 0.8 wt%, about 0.4 wt% of the self-assembled copolymer. To about 0.7 wt%, about 0.5 wt% to about 0.6 wt%, about 0.2 wt% to about 1.0 wt%, about 0.3 wt% to about 1.0 wt%, about 0.4 wt% to about 1.0 wt%, about 0.5 wt% To about 1.0 wt%, about 0.1 wt% to about 0.9 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.7 wt%, about 0.1 wt% to about 0.6 wt%, or about 0.1 wt% % To about 0.5% by weight, but is not limited thereto.

Subsequently, (b) coating the prepared reverse micelle solution to prepare a self-assembled biblock copolymer reverse micelle thin film.

The method of coating the reverse micelle solution may be performed by a method known in the art, for example, a coating method selected from the group consisting of spin coating, spray coating, dip coating, flow coating, and combinations thereof. It may be performed by, but is not limited thereto.

Subsequently, (c) induce reconstitution of the prepared reverse micelle thin film.

By immersing the prepared reverse micelle thin film in a solution having a selectivity to the P4VP block it is possible to rearrange the P4VP block chains to induce the generation of pores through the opening of the reverse micelles. As a solution for inducing reconstitution, for example, non-polar solvents such as alcohol and water and acidic solutions may be used, but are not limited thereto. For example, an acidic solution may be used among them, but is not limited thereto. The reverse micelle thin film may be immersed, for example, for about 20 minutes, but is not limited thereto (see Experimental Example 1).

Then, (d) selectively adsorbs the gold nanoparticles stabilized by the citrate ligand on the reconstituted reverse micelle thin film.

The reconstituted reverse micelle thin film is immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, thereby allowing the gold nanoparticles to selectively bind to P4VP exposed on the surface. In this case, the aqueous solution of gold nanoparticles may have, for example, acidity 6, but is not limited thereto.

The reconstituted reverse micelle thin film can be immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, for example, from about 10 minutes to about 24 hours, and local surface plasmon resonance binding by controlling the degree of adsorption. You can control the phenomenon.

Next, a method for producing a gold nanoparticle pattern according to the type II method will be described.

(a) The self-assembled copolymer was dissolved in a solvent to prepare a reverse micelle solution.

The self-assembled copolymer is an amphiphilic diblock copolymer, which can form reverse micelles in a solution when dissolved in a solvent selective to only one block. As the diblock copolymer, polystyrene-block-polyvinylpyridine can be used, for example polystyrene-block-poly (4-vinylpyridine) and polystyrene-block-poly (2-vinylpyridine), and More preferably. As the solvent, a solvent having a selective affinity for the styrene block in the diblock copolymer may be used. For example, toluene, chloroform, tetrahydrofuran (THF), etc. may be used, and among them, toluene may be used. desirable.

The reverse micelle solution may contain, for example, about 0.1 wt% to about 1.0 wt% of the self-assembled copolymer, but is not limited thereto. If the self-assembled copolymer is less than about 0.1% by weight, there is a problem in that a uniform monomolecular film without defects is not produced, and when the self-assembled copolymer is more than about 1.0% by weight, a monomolecular film is not produced. The reverse micelle solution may comprise, for example, about 0.1 wt% to about 1.0 wt%, about 0.2 wt% to about 0.9 wt%, about 0.3 wt% to about 0.8 wt%, about 0.4 wt% of the self-assembled copolymer. To about 0.7 wt%, about 0.5 wt% to about 0.6 wt%, about 0.2 wt% to about 1.0 wt%, about 0.3 wt% to about 1.0 wt%, about 0.4 wt% to about 1.0 wt%, about 0.5 wt% To about 1.0 wt%, about 0.1 wt% to about 0.9 wt%, about 0.1 wt% to about 0.8 wt%, about 0.1 wt% to about 0.7 wt%, about 0.1 wt% to about 0.6 wt%, or about 0.1 wt% % To about 0.5% by weight, but is not limited thereto.

Subsequently, (b) coating the prepared reverse micelle solution to prepare a self-assembled biblock copolymer reverse micelle thin film.

The method of coating the reverse micelle solution may be performed by a method known in the art, for example, a coating method selected from the group consisting of spin coating, spray coating, dip coating, flow coating, and combinations thereof. It may be performed by, but is not limited thereto.

Subsequently, (c ′) induces reconstitution of the prepared reverse micelle thin film and simultaneously adsorbs gold nanoparticles stabilized by citrate ligand.

By immersing the prepared reverse micelle thin film in a solution having a selectivity to the P4VP block it is possible to rearrange the P4VP block chains to induce the generation of pores through the opening of the reverse micelles. As a solution for inducing reconstitution, for example, non-polar solvents such as alcohol and water and acidic solutions may be used, but are not limited thereto. For example, an acidic solution may be used among them, but is not limited thereto. The reverse micelle thin film may be immersed, for example, for about 20 minutes, but is not limited thereto.

The reconstituted reverse micelle thin film is immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, thereby allowing the gold nanoparticles to selectively bind to P4VP exposed on the surface. At this time, the aqueous solution of the gold nanoparticles, for example, may have an acidity 6, but is not limited thereto.

The reconstituted reverse micelle thin film can be immersed in an aqueous solution containing gold nanoparticles stabilized by a citrate ligand, for example, from about 10 minutes to about 24 hours, and local surface plasmon resonance binding by controlling the degree of adsorption. You can control the phenomenon.

The present application provides a pattern of gold nanoparticles exhibiting a unique topical surface plasmon resonance binding phenomenon prepared according to the method.

The pattern of the gold nanoparticles prepared according to the present invention can easily control the shape and arrangement of the gold nanoparticle pattern by changing the molecular weight or the relative volume fraction between blocks of the diblock copolymer, and thus the local surface plasmon resonance coupling You can control the phenomenon.

In addition, the pattern of the gold nanoparticles prepared according to the present application can easily control the shape and arrangement of the gold nanoparticle pattern by changing the size of the gold nanoparticles, it is possible to control the local surface plasmon resonance coupling phenomenon.

In addition, the pattern of the gold nanoparticles prepared according to the present invention can be applied to the surface of the surface sensitized Raman scattering which can increase the intensity of Raman scattering of the molecules adsorbed to the gold nanoparticles (see Experimental Example 5).

Furthermore, a regularly arranged array of gold nanoparticles can be applied to optical sensing (see Experimental Example 6).

Specifically, an example of applying an array of gold nanoparticles prepared using a self-assembled copolymer as a template to protein sensing can be seen (see Experimental Example 5 and Experimental Example 6).

Therefore, the pattern of the gold nanoparticles of the present application can control the shape and arrangement of the pattern by using a diblock copolymer having a different molecular weight or by varying the size of the gold nanoparticles, thereby resulting in local surface plasmon resonance coupling The phenomenon can be confirmed.

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present application is not limited thereto.

[ Example ]

< Example  1> Control and Preparation of Gold Nanoparticle Patterns by "Type I" Method 1

Step (a): containing self-assembled double block copolymer Reverse mice  Solution preparation

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 (b): Self-Assembled Diblock Copolymer Reverse mice  Manufacture of thin films

The self-assembled copolymer reverse micelle thin film was prepared by spin coating the self-assembled copolymer reverse micelle solution prepared in step (a) at 2000 rpm for 60 seconds.

Step (c): Reverse mice  Reconstruction of thin film

The reverse micelle thin film prepared in step (b) was immersed in an aqueous solution containing 0.9 wt% hydrochloric acid for 20 minutes to induce reconstitution of reverse micelles.

Step (d): Citrate In the ligand  Adsorption of Stabilized Gold Nanoparticles

The reverse micelle thin film reconstituted in step (c) was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 10 minutes to adsorb gold nanoparticles stabilized by citrate ligand.

< Example  2> Control and Preparation of Gold Nanoparticle Patterns by the "Type I" Method 2

Example 1 except that the reverse micelle thin film reconstituted in step (d) of Example 1 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 1 hour. To make.

< Example  3> Control and Preparation of Gold Nanoparticle Patterns by "Type I" Method 3

The reverse micelle thin film reconstituted in step (d) of Example 1 was the same as Example 1 except that it was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 1.5 hours. To make.

< Example  4> Control and Preparation of Gold Nanoparticle Patterns by the "Type I" Method 4

Same as Example 1 except that the reverse micelle thin film reconstituted in step (d) of Example 1 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 2 hours. To make.

< Example  5> Control and Preparation of Gold Nanoparticle Patterns by the "Type I" Method 5

Example 1 except that the reverse micelle thin film reconstituted in step (d) of Example 1 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 3 hours. To make.

< Example  6> Control and Preparation of Gold Nanoparticle Patterns by the "Type I" Method 6

The reverse micelle thin film reconstituted in step (d) of Example 1 was the same as Example 1 except that it was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 6 hours. To make.

< Example  7> Control and Preparation of Gold Nanoparticle Patterns by the "Type I" Method 7

Example 1 except that the reverse micelle thin film reconstituted in step (d) of Example 1 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 24 hours. To make.

< Example  8> Control and Preparation of Gold Nanoparticle Patterns by the "Type II" Method 1

Step (a): containing self-assembled copolymer Reverse mice  Solution preparation

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 (b): Self-Assembly Copolymer Reverse mice  Manufacture of thin films

The self-assembled copolymer reverse micelle thin film was prepared by spin coating the self-assembled copolymer reverse micelle solution prepared in step (a) at 2000 rpm for 60 seconds.

step ( c ' ): Reverse mice  Reconstruction of thin film and Citrate In the ligand  Adsorption of Stabilized Gold Nanoparticles

The reverse micelle thin film prepared in step (b) was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 10 minutes to flow the reconstitution of reverse micelles and at the same time stabilized by citrate ligand. Gold nanoparticles were adsorbed.

< Example  9> Control and Preparation of Gold Nanoparticle Patterns by the "Type II" Method 2

In the same manner as in Example 8 except that the reverse micelle thin film of Example 8 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 30 minutes. Prepared.

< Example  10> Control and Preparation of Gold Nanoparticle Patterns by the "Type II" Method 3

In the same manner as in Example 8 except that the reverse micelle thin film of Example 8 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 1 hour. Prepared.

< Example  11> Control and Preparation of Gold Nanoparticle Patterns by the "Type II" Method 4

In the same manner as in Example 8 except that the reverse micelle thin film of Example 8 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 3 hours. Prepared.

< Example  12> Control and Preparation of Gold Nanoparticle Patterns by the "Type II" Method 5

In the same manner as in Example 8 except that the reverse micelle thin film of Example 8 was immersed in an aqueous solution of acidity 6 containing gold nanoparticles stabilized by citrate ligand for 24 hours. Prepared.

< Experimental Example  1> Control and Preparation of Gold Nanoparticle Patterns by "Type I" Method

The following experiments were performed to reveal that the reverse micelles of the self-assembled copolymers were reconstituted by the "Type I" method and to reveal that the gold nanoparticles were adsorbed.

The surface of the thin film of Example 1 was observed with an atomic force microscope (AFM), and is shown in FIG. 2. More specifically, the surface of the thin film of step (b) of Example 1 was observed in an atomic force microscope (AFM) and is shown in Figure 2 (a), the surface of the thin film of step (c) of Example 1 It was observed in the atomic force microscope (AFM) is shown in Figure 2 (b).

As can be seen in FIG. 2 (a), polystyrene-block-poly (4-vinylpyridine) reverse micelles in a regularly ordered arrangement could be observed. In addition, as can be seen in Figure 2 (b), it was possible to observe the reconstituted reverse micelles. The acidic aqueous solution component used in Example 1 was rearranged the chain of 4-vinylpyridine block to induce reconstitution of reverse micelles it can be confirmed that the nano-pores are formed. The acidic aqueous solution was selective for the 4-vinylpyridine block and was able to induce the adsorption of gold nanoparticles stabilized by the citrate ligand by protonating the 4-vinylpyridine block simultaneously with opening of reverse micelles.

The surfaces of the thin films were observed by field emission scanning electron microscopy (FESEM) for Examples 1, 2, 3, 4, 5, 6, and 7, respectively, and are shown in FIGS. 3 (a) to 3 (g), respectively. More specifically, the surface of step (d) of Examples 1, 2, 3, 4, 5, 6, and 7 was observed by field emission scanning electron microscopy (FESEM), and then FIGS. 3 (a) and 3 ( b), FIG. 3 (c), FIG. 3 (d), FIG. 3 (e), FIG. 3 (f) and FIG. 3 (g).

As can be seen in Figure 3, it was confirmed that the gold nanoparticles are adsorbed on the reconstituted reverse micelle thin film. Furthermore, as the immersion time of the reconstituted reverse micelle thin film became longer, the number of gold nanoparticles adsorbed increased. However, it can be seen from FIG. 3 that the adsorption of gold nanoparticles by the “Type I” method does not have regularity. Gold nanoparticles were partially deposited not only in the reconstituted 4-vinylpyridine but also in the styrene region, and as the immersion time increased, the gold nanoparticles were randomly adsorbed on the entire surface of the reconstituted reverse micelle thin film. In addition, the average distance between the gold nanoparticles is close, it can be seen that the pattern of the clusters connected to each other.

< Experimental Example  2> localized surface of the gold nanoparticle pattern produced by the "Type I" method Plasmon  Resonance coupling phenomenon

The following experiments were conducted to investigate localized surface plasmon resonance binding of gold nanoparticle patterns prepared by the "Type I" method.

The UV-visible spectrophotometer graphs of Examples 1, 2, 3, 4, 5, 6, and 7 measured to measure local surface plasmon resonance coupling of gold nanoparticle patterns are shown in FIG. 4.

As can be seen in FIG. 4, the local surface plasmon coplanar peak of the gold nanoparticles can be observed around the 525 nm wavelength. In addition, as the immersion time was longer, the position of the local surface plasmon resonance peak wavelength was shifted to longer wavelength, and it was clearly confirmed that a new peak derived by the binding phenomenon appeared. The red mark represents the local surface plasmon peak of the gold nanoparticles and the yellow mark represents the new binding peak. It can be seen that this is a binding peak resulting from the interference of the flock-type gold nanoparticles formed as the immersion time is longer. The shift to the long wavelength of the local surface plasmon resonance peak and the generation of new binding peaks are phenomena showing that the shape and arrangement of the gold nanoparticles are changed and thus the optical properties of the final pattern are changing. It can be seen that the same phenomenon can be seen from the image of the microscope (FESEM).

< Experimental Example  3> Control and Preparation of Gold Nanoparticle Patterns by "Type II" Method

The following experiments were performed to reveal that the reverse micelles of the self-assembled copolymers were reconstituted by the "Type II" method and gold nanoparticles were adsorbed.

For Examples 8, 9, 10, 11 and 12, the surface of the thin film was observed by field emission scanning electron microscopy (FESEM) and shown in FIGS. 5 (a) to 5 (e), respectively. More specifically, the surface of step (c ') of Examples 8, 9, 10, 11, and 12 was observed with a field emission scanning electron microscope (FESEM), and FIGS. 5 (a), 5 (b), and FIG. 5 (c), 5 (d) and 5 (e) are shown.

As can be seen in Figure 5, it was confirmed that the gold nanoparticles are adsorbed on the reconstituted reverse micelle thin film by the "Type II" method. Furthermore, the longer the immersion time of the reverse micelle thin film, the higher the number of adsorbed gold nanoparticles. In addition, unlike the "type I" method, the adsorption of gold nanoparticles by "type II" can be seen that the regularity. An aqueous solution of acidity 6 containing gold nanoparticles may induce reconstitution of reverse micelles and simultaneously bind gold nanoparticles to open 4-vinylpyridine.

< Experimental Example  4> Topical surface of the gold nanoparticle pattern produced by the "Type II" method Plasmon  Resonance coupling phenomenon

The following experiments were conducted to investigate localized surface plasmon resonance binding of gold nanoparticle patterns prepared by the "Type II" method.

The UV-visible spectrophotometer graphs of Examples 8, 9, 10, 11, and 12 measured to measure localized surface plasmon resonance coupling of gold nanoparticle patterns are shown in FIG. 6.

As can be seen in Figure 6, the local surface plasmon coplanar peak of the gold nanoparticles could be observed around the 525 nm wavelength. In addition, as the immersion time is longer, the location of the local surface plasmon resonance peak wavelength is weakly shifted to longer wavelengths, and new binding peaks are weakly generated. The red mark represents the local surface plasmon peak of the gold nanoparticles and the yellow mark represents the new binding peak. It should be noted that the local surface plasmon resonance properties exhibited by the pattern of gold nanoparticles produced by the "Type II" method differ from those exhibited by the gold nanoparticle pattern produced by the "Type I" method. That is, even if the immersion time is prolonged, it can be seen that gold nanoparticles are selectively adsorbed to 4-vinylpyridine along a regular array. The intensity of the new binding peak is relatively weak compared to "Type I", while absorption is limited because the interference between each adsorbed gold nanoparticles confined within the 4-vinylpyridine region and does not form clusters even with longer immersion times, while absorbing The increase in the intensity of the peak indicates that the field of the local surface plasmon resonance peak appears strongly. The shift to the longer wavelength of the local surface plasmon resonance peak and the increase in the field are simply phenomena showing the change in the arrangement of the gold nanoparticles, which is the same phenomenon as can be seen from the image of the field emission scanning electron microscope (FESEM) of FIG. 5. Able to know.

< Experimental Example  5> Surface-sensitized Raman scattering experiments of gold nanoparticle patterns produced by the "Type I" and "Type II" methods, respectively

The following experiment was carried out to see if the surface of the Raman scattering of the molecules adsorbed on the gold nanoparticle pattern produced by the "Type I" and "Type II" method can be applied to the surface.

Substrates with gold nanoparticle patterns prepared by the "Type I" and "Type II" methods were immersed in an ethanol solution containing 1 mM para-aminothiophenol molecules for 30 minutes to adsorb the molecules on the surface of the gold nanoparticles. Were induced, and the unadsorbed molecules were removed. The degree of surface sensitization Raman scattering of the adsorption molecules was measured using a Macro Raman spectrum analyzer with a 632.8 nm wavelength.

Surface sensitized Raman scattering graphs measured for measuring surface sensitized Raman scattering properties of gold nanoparticle patterns for Examples 1, 2, 5 and 7 prepared by the “Type I” method are shown in FIG. 7.

Surface sensitized Raman scattering graphs measured for measuring surface sensitized Raman scattering properties of gold nanoparticle patterns for Examples 8, 10, 11 and 12 prepared by the “Type II” method are shown in FIG. 8.

7 and 8 are graphs showing the surface sensitized Raman scattering of para-aminothiophenol molecules, and the sensitization of the y-axis shows the intensity of Raman scattering of para-aminothiophenol molecules. It shows strength.

As can be seen in Figures 7 and 8, the gold nanoparticle pattern prepared by the "Type I" and "Type II" method can be applied as a surface for measuring the surface sensitized Raman scattering characteristics, commonly adsorbed It was confirmed that the sensitization of the surface sensitization Raman scattering of the molecules is gradually increased as the immersion time at 1100, 1200, 1400, 1500, and 1600 cm ^-1 wavenumber. As the immersion time increases, the number of gold nanoparticles that can adsorb on the surface increases, and as a result, the interference between gold nanoparticles increases, so that the intensity of the surface sensitization Raman scattering of the molecules adsorbed on the surface of the gold nanoparticles gradually increases. It can be seen that the increase. It should be noted that the surface of the gold nanoparticle pattern produced by the "Type I" method has a larger increase in the surface sensitization Raman scattering of the adsorption molecules than the surface of the gold nanoparticle pattern produced by the "Type II" method. It was confirmed that it was. That is, as described in <Experimental Example 2>, adsorption on the surface of the "type I" that forms a bunch of gold nanoparticles as the immersion time is longer, so that the interference between the gold nanoparticles occurs more strongly It can be seen that the Raman scattering degree of one molecule is further increased.

< Experimental Example  6> Proteins Using Gold Nanoparticle Arrays Sensing

The following experiments were conducted to determine the sensing capability of using gold nanoparticle arrays prepared from self-assembled copolymer templates as sensors for detecting proteins.

A schematic diagram of preparing a gold nanoparticle array from a self-assembled copolymer template is shown in FIG. 9 (a). Oxygen plasma treatment removes the self-assembled copolymer template and produces an array of aligned gold nanoparticles while reducing precursors of the gold nanoparticles.

An example in which an array of gold nanoparticles prepared from a self-assembled copolymer template can be used as a sensor for detecting a protein will be described as an example. In FIG. 9 (b), MUA (mercaptoundecanoic acid) and OT (octanethiol, octanethiol) layers were deposited on the array of gold nanoparticles, and a schematic diagram showing the binding of biotin and streptavidin was shown. MUA and OT are self-assembled monolayers for biotin introduction. The introduced biotin can detect streptavidin by selectively binding to streptavidin. Binding of streptavidin was confirmed from the shift of local surface plasmon resonance peaks of gold nanoparticles. As can be seen in FIG. 10, it was found that the wavelength at which the local surface plasmon resonance peak of the gold nanoparticles is shifted to the long wavelength at each step. This indicates that the local surface plasmon resonance of the gold nanoparticles is changed by the binding of the material, that is, the change in the surrounding environment. It is an example showing that the binding of a substance can be predicted from the shift of the local surface plasmon resonance peak of gold nanoparticles.

It will be understood by those of ordinary skill in the art that the foregoing description of the embodiments is for illustrative purposes and that those skilled in the art can easily modify the invention without departing from the spirit or essential characteristics of the present invention. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims rather than the detailed description, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included in the scope of the present invention .

Claims (14)

(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution;
(b) coating the reverse micelle solution on a solid substrate to prepare a self-assembled biblock copolymer reverse micelle thin film;
(c) inducing reconstruction of the reverse micelle thin film by immersing the reverse micelle thin film in a nonpolar solvent or an acidic solution; And
(d) adsorbing gold nanoparticles stabilized by citrate ligand on the reconstituted reverse micelle thin film
A method of producing a gold nanoparticle pattern comprising a.
(a) dissolving the self-assembled diblock copolymer in a solvent to prepare a reverse micelle solution;
(b) coating the reverse micelle solution on a solid substrate to prepare a self-assembled biblock copolymer reverse micelle thin film; And
(c ') inducing the reconstitution of the reverse micelle thin film by immersing the reverse micelle thin film in an apolar solvent or an acidic solution and adsorbing gold nanoparticles stabilized by citrate ligand.
A method of producing a gold nanoparticle pattern comprising a.
3. The method according to claim 1 or 2,
The self-assembled diblock copolymer is a method of producing a gold nanoparticle pattern comprising an amphiphilic diblock copolymer.
The method of claim 3, wherein
The amphiphilic diblock copolymers are polystyrene-block-poly (4-vinylpyridine) (PS-b-P4VP), polystyrene-block-poly (2-vinylpyridine) (PS-b-P2VP), polystyrene-block- Gold nanoparticle pattern, including those selected from the group consisting of poly (ethylene oxide) (PS-b-PEO), polystyrene-block-poly (acrylic acid) (PS-b-PAA), and combinations thereof Manufacturing method.
3. The method according to claim 1 or 2,
Wherein the solvent is to dissolve only one block of the self-assembly diblock copolymer, gold nanoparticle pattern manufacturing method.
The method of claim 5, wherein
Wherein said solvent comprises one selected from the group consisting of chloroform, tetrahydrofuran (THF), toluene, and combinations thereof.
3. The method according to claim 1 or 2,
The reverse micelle solution contains 0.1 wt% to 1.0 wt% of the self-assembled diblock copolymer.
3. The method according to claim 1 or 2,
The solid substrate is a method of producing a gold nanoparticle pattern, comprising a silicon wafer.
3. The method according to claim 1 or 2,
The reconstruction of the reverse micelle thin film is induced by immersing in a solvent for selectively dissolving only one block of the self-assembled diblock copolymer, gold nanoparticle pattern manufacturing method.
The method of claim 9,
Wherein said solvent comprises one selected from the group consisting of alcohol, water, acidic solutions, and combinations thereof.
The method of claim 9,
The immersion time is 10 minutes to 24 hours, method of producing a gold nanoparticle pattern.
3. The method according to claim 1 or 2,
The gold nanoparticles will include a gold nanoparticles modified by a negatively charged molecule, gold nanoparticle pattern manufacturing method.
A nanostructure, prepared according to the method of claim 1 or 2, comprising a gold nanoparticle pattern exhibiting localized surface plasmon resonance binding phenomena.
A sensor comprising the nanostructures according to claim 13.

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