Chiral plasmonic hybrid structure and manufacturing method therefor

Abstract

The present application relates to a chiral plasmonic hybrid structure and a manufacturing method therefor. The chiral plasmonic hybrid structure according to embodiments of the present application has excellent chiral optical properties, and thus can be applied as a promising material for a circular polarization sensing device, an anti-counterfeiting system, a circular polarization filter, a display, and the like, which are next-generation application fields.

Description

Chiral plasmonic hybrid structure and method for preparing the same

[0001] The present invention relates to a chiral plasmonic hybrid structure and a method for manufacturing the same.

[0002] The field of chiral materials has grown significantly, inspired by the abundance of chiral structures found in nature. Among these, chiral supramolecular assemblies have attracted considerable attention due to their complexity and diversity in structural and chiral optical properties. These assemblies derive their supramolecular chirality from the asymmetric arrangement of constituent molecules via non-covalent bonds, which serve as bridges for the hierarchical transfer of chirality. Supramolecular chirality can arise from the self-assembly of chiral molecules, the co-assembly of chiral and achiral molecules, or the spontaneous asymmetric self-assembly of achiral molecules under chiral environmental influences or conditions. Careful control of several variables allows for manipulation of the generation of supramolecular chirality. The kinetics and thermodynamics of chiral supramolecular assemblies can be controlled by carefully designing the molecular structures of the building blocks, or by controlling dynamic non-covalent interactions, solvent effects, stoichiometry, temperature, and time. This has led to the creation of various chiral supramolecular structures, such as helical nanotubes, helical microtoroids, and spiral tubes. Interestingly, chiral supramolecular assembly can also be induced in systems composed solely of achiral molecules. This can be achieved by applying external stimuli such as asymmetric mechanical forces, circularly polarized light irradiation, or magnetic forces. This extensive exploration of chiral supramolecular assembly offers exciting prospects for the development of advanced materials and functional systems with interesting properties and applications in various research fields.

[0003] Plasmonic properties refer to the strong light-matter interaction that occurs when nanometer-sized metal particles interact with light through localized surface plasmon resonance, resulting in enhanced optical phenomena. Representative fabrication methods for chiral plasmonic structures, which are metal structures that integrate plasmonic properties and chirality, include methods using chiral surface ligands to transfer chirality from chiral molecules to plasmonic structures; vapor deposition methods such as physical vapor deposition (top-down approach); and methods using chiral templates to asymmetrically align chiral nanoparticles (bottom-up approach). These synthetic methods are simple and effective ways to create chiral plasmonic hybrid structures with diverse compositions and structures. While supramolecular assembly scaffolds can induce diverse chiral arrangements or configurations of achiral nanostructures (Ag or Au NPs), they suffer from weak chiral optical activity, ineffective evolution of plasmonic chirality, and structural instability, which limit their applications in various important fields such as catalysis, sensing, and optics.

[0004] The present invention provides a chiral plasmonic hybrid structure and a method for manufacturing the same.

[0005] However, the problems that the present invention seeks to solve are not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0006] A first aspect of the present invention provides a chiral plasmonic hybrid structure comprising an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; a chiral additive; and chiral plasmonic nanoparticles.

[0007] A second aspect of the present invention provides a method for preparing a chiral plasmonic hybrid structure, comprising: preparing a first solution by adding an achiral star block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; and a chiral additive to a first solvent; preparing a second solution by adding an achiral star block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer, a reducing agent, and a gold precursor to a second solvent; and mixing and heat-treating the first solution and the second solution to obtain a chiral plasmonic hybrid structure.

[0008] The third aspect of the present invention provides a material comprising a chiral plasmonic hybrid structure according to the first aspect and applicable to a device.

[0009] The chiral plasmonic hybrid structure according to the embodiments of the present invention has excellent chiral optical properties and can be applied as a promising material in next-generation applications such as circularly polarized light detection devices, anti-counterfeiting systems, circularly polarized light filters, and displays.

[0010] Conventional methods for synthesizing chiral plasmonic structures using chiral supramolecular templates have limited chirality transfer due to an inefficient assembly process, resulting in insufficient or weak expression of plasmonic chiral optical properties. However, the method for manufacturing chiral plasmonic hybrid structures according to the embodiments of the present disclosure allows gold nanoparticles to be firmly and stably formed within a star-shaped block copolymer template, thereby acting as effective building blocks for chiral co-assembly. Effective chiral co-assembly between star-shaped PAA-b-PS hydrogen-bonded with R / S-mandelic acid and gold nanoparticles formed within the star-shaped PAA-b-PS effectively enhances the transfer and expression of plasmonic chiral optical properties, thereby achieving a larger asymmetry factor value compared to conventional synthetic methods.

[0011] The method for manufacturing a chiral plasmonic hybrid structure according to the embodiments of the present invention is a co-assembly based on a nonlinear block copolymer, and can be controlled according to various variables such as volume ratio, solvent, and temperature, so that the structure and optical properties of the manufactured chiral plasmonic hybrid structure can be easily adjusted.

[0012] The method for manufacturing a chiral plasmonic hybrid structure according to the embodiments of the present invention can enable large-scale mass production based on a simple synthesis process by utilizing the assembly characteristics of a block copolymer.

[0013] Figure 1 is a schematic diagram of a method for manufacturing a chiral plasmonic hybrid structure according to one embodiment of the present invention.

[0014] FIG. 2 is a transmission electron microscope (TEM) image of a star-shaped block copolymer template in which gold nanoparticles are synthesized in one embodiment of the present invention.

[0015] Figure 3 is an absorption spectrum of a star-shaped block copolymer template in which gold nanoparticles are synthesized in one embodiment of the present invention.

[0016] FIG. 4 is an X-ray diffraction graph of a star-shaped block copolymer template in which gold nanoparticles are synthesized in one embodiment of the present invention.

[0017] FIG. 5 shows the circular dichroism and absorption spectra of fiber-like chiral plasmonic hybrid structures (PS-b-PAA / R-MA / Au and PS-b-PAA / S-MA / Au) in one embodiment of the present invention.

[0018] FIG. 6 is an asymmetric factor graph of a chiral plasmonic hybrid structure in the form of a fiber, in one embodiment of the present invention.

[0019] FIGS. 7A to 7F are scanning electron microscope (SEM) images of a fiber-shaped chiral plasmonic hybrid structure in one embodiment of the present invention.

[0020] FIGS. 8A and 8B are X-ray diffraction graphs for a chiral plasmonic hybrid structure in the form of a fiber and each co-assembled component in one embodiment of the present invention.

[0021] FIG. 9 is a circular dichroism and absorption spectra of rod-like chiral plasmonic hybrid structures (PS-b-PAA / R-MA / Au and PS-b-PAA / S-MA / Au) in one embodiment of the present invention.

[0022] FIG. 10 is an asymmetric factor graph of a rod-shaped chiral plasmonic hybrid structure in one embodiment of the present invention.

[0023] Figures 11a to d are SEM images of a rod-shaped chiral plasmonic hybrid structure in one embodiment of the present invention.

[0024] FIG. 12 is an X-ray diffraction graph of a rod-shaped chiral plasmonic hybrid structure (block copolymer / R-MA / Au NP and block copolymer / S-MA / Au NP, wherein the block copolymer is PS-b-PAA) in one embodiment of the present invention.

[0025] FIG. 13 is a circular dichroism and absorption spectrum of a chiral plasmonic hybrid structure prepared using a linear block copolymer (PS-b-P4VP) in one embodiment of the present invention.

[0026] FIG. 14 is an asymmetric factor graph of a chiral plasmonic hybrid structure prepared using a linear block copolymer (PS-b-P4VP) in one embodiment of the present invention.

[0027] Figures 15a and b are SEM images of a chiral plasmonic hybrid structure manufactured using a linear block copolymer (PS-b-P4VP) in one embodiment of the present invention.

[0028] Hereinafter, with reference to the attached drawings, implementation examples and embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. However, the present invention may be implemented in various different forms and is not limited to the implementation examples and embodiments described herein. In addition, in the drawings, parts irrelevant to the description have been omitted to clearly explain the present invention, and similar parts have been designated with similar drawing reference numerals throughout the specification.

[0029] Throughout this specification, when a part is said to be "connected" to another part, this includes not only cases where it is "directly connected" but also cases where it is "electrically connected" with another element in between.

[0030] Throughout this specification, when it is said that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the two elements.

[0031] Throughout this specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise specifically stated.

[0032] The terms "about," "substantially," and the like used in this specification are used in a meaning that is at or close to the numerical value when manufacturing and material tolerances inherent in the meanings mentioned are presented, and are used to prevent unscrupulous infringers from unfairly exploiting the disclosure in which exact or absolute values ​​are mentioned to aid understanding of the present application.

[0033] The terms “step of ~” or “step of ~” as used throughout this specification do not mean “step for ~.”

[0034] Throughout this specification, the term "combination(s) thereof" included in the expressions in the Makushi format means one or more mixtures or combinations selected from the group consisting of the components described in the expressions in the Makushi format, and means including one or more selected from the group consisting of said components.

[0035] Throughout this specification, references to “A and / or B” mean “A or B, or A and B.”

[0036] Below, the implementation examples of the present invention are described in detail, but the present invention may not be limited thereto.

[0037] A first aspect of the present invention provides a chiral plasmonic hybrid structure comprising an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; a chiral additive; and chiral plasmonic nanoparticles.

[0038] In one embodiment of the present invention, the core block polymer, polyacrylic acid, and the chiral additive may non-covalently interact through hydrogen bonding.

[0039] In one embodiment of the present invention, the core block polymer and the chiral additive may interact non-covalently, so that the chirality of the chiral additive is transferred to the core block polymer.

[0040] In one embodiment of the present invention, the preferred handedness of the chiral plasmonic hybrid structure may be determined depending on the chirality of the chiral additive. For example, when the chiral additive is mandelic acid (MA), the chiral plasmonic hybrid structure loaded with S-MA may produce a left-handed structure, and the chiral plasmonic hybrid structure loaded with R-MA may produce a right-handed structure.

[0041] In one embodiment of the present invention, the shell block polymer may be a hydrophobic polymer.

[0042] In one embodiment of the present invention, the hydrophobic polymer may include one or more selected from polystyrene, polyethylene, polypropylene, polybutadiene, polyaniline, polythiophene, poly(phenylene vinylene), and derivatives thereof, but may not be limited thereto.

[0043] In one embodiment of the present invention, the polythiophene may be a polyalkylthiophene including, but not limited to, poly(3-ethylthiophene), poly(3-butylthiophene), poly(3-pentylthiophene), or poly(3-hexylthiophene).

[0044] In one embodiment of the present invention, the chiral additive may include a chiral carbon having molecular chirality; and a carboxylic acid group and / or a hydroxyl group as a functional group capable of multiple hydrogen bonds with the acrylic acid (AA) repeating unit of the polyacrylic acid.

[0045] In one embodiment of the present invention, the chiral additive may include one or more selected from mandelic acid, tartaric acid, aspartic acid, tyrosine, ibuprofen, and hydroxymandelic acid, but may not be limited thereto.

[0046] In one embodiment of the present invention, the achiral star-shaped block copolymer may have a star-shaped structure including a plurality of arms extending from the core block polymer. The achiral star-shaped block copolymer may have a star-shaped structure including 21 arms extending from the core block polymer.

[0047] In one embodiment of the present invention, the achiral star-shaped block copolymer may include a plurality of arms extending from the core block polymer, and the shell block polymer may be formed by bonding to each of the plurality of arms.

[0048] In one embodiment of the present invention, the achiral star-shaped block copolymer may be an amphiphilic polymer comprising a hydrophilic core block polymer and a hydrophobic shell block polymer. In one embodiment of the present invention, the core block polymer is a hydrophilic polymer and the shell block polymer is a hydrophobic polymer, and when forming a chiral plasmonic hybrid structure through co-assembly, phase separation may occur due to chemical incompatibility between the core block polymer and the shell block polymer.

[0049] In one embodiment of the present invention, the achiral star-shaped block copolymer can form multiple hydrogen bonds with a chiral additive and provide a unimolecular micelle environment linked by covalent bonds. Therefore, the chiral plasmonic hybrid structure of the present invention has a significantly higher yield than a chiral molecular structure including a conventional linear block copolymer, has a distinct helical direction of the supramolecular structure transferred from molecular chirality, and has the characteristics of strong supramolecular chirality occurring over a wide wavelength range from ultraviolet to visible light. The absolute value of the asymmetry factor can be about 0.02 to about 0.2, for example, -0.2 for R-MA and +0.14 for S-MA at 500 nm.

[0050] In one embodiment of the present invention, the volume ratio of the core block polymer and the shell block polymer may be about 1:1 to about 1:4, but may not be limited thereto. In one embodiment of the present invention, the volume ratio of the core block polymer and the shell block polymer may be about 1:1 to about 1:4, about 1:1 to about 1:3, or about 1:1 to about 1:2, but may not be limited thereto.

[0051] In one embodiment of the present invention, the chiral plasmonic nanoparticles may include one or more selected from Au, Ag, Pt, Pd, Rh, Cu, Al, Mg, In, Ga, and Ni. In one embodiment of the present invention, the chiral plasmonic nanoparticles may include Au.

[0052] In one embodiment of the present disclosure, the diameter of the chiral plasmonic nanoparticle may be about 4 nm to about 20 nm. In one embodiment of the present disclosure, the diameter of the chiral plasmonic nanoparticle may be about 4 nm to about 20 nm, about 4 nm to about 15 nm, about 4 nm to about 12 nm, about 4 nm to about 10 nm, about 6 nm to about 20 nm, about 6 nm to about 15 nm, about 6 nm to about 12 nm, or about 6 nm to about 10 nm. In one embodiment of the present disclosure, the diameter of the chiral plasmonic nanoparticle may be about 8 nm.

[0053] In one embodiment of the present invention, the chiral plasmonic hybrid structure may be in the form of a fiber or a rod.

[0054] A second aspect of the present invention provides a method for preparing a chiral plasmonic hybrid structure, comprising: preparing a first solution by adding an achiral star block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; and a chiral additive to a first solvent; preparing a second solution by adding an achiral star block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer, a reducing agent, and a gold precursor to a second solvent; and mixing and heat-treating the first solution and the second solution to obtain a chiral plasmonic hybrid structure.

[0055] Detailed descriptions of parts that overlap with the first aspect of the present application have been omitted, but the contents described in the first aspect of the present application may be equally applied even if the description is omitted in the second aspect of the present application.

[0056] In one embodiment of the present invention, the chiral plasmonic hybrid structure may have a fiber shape or a rod shape depending on the type of the first solvent.

[0057] In one embodiment of the present invention, the molar ratio of the acrylic acid repeating unit of the polyacrylic acid to the chiral additive may be about 1:1 to about 1:3, but may not be limited thereto. In one embodiment of the present invention, the molar ratio of the acrylic acid repeating unit of the polyacrylic acid to the chiral additive may be about 1:1 to about 1:3, about 1:1 to about 1:2.5, about 1:1 to about 1:2, about 1:1.5 to about 1:3, about 1:1.5 to about 1:2.5, or about 1:1.5 to about 1:2, but may not be limited thereto.

[0058] In one embodiment of the present invention, the first solvent may include at least one selected from dimethylformamide, toluene, tetrahydrofuran, ethyl acetate, 1,4-dioxane, dimethyl sulfoxide, acetonitrile, acetone, ethanol, and methanol.

[0059] In one embodiment of the present invention, (i) when the first solvent is dimethylformamide alone, the chiral plasmonic hybrid structure may be formed in a fiber shape, and (ii) when the first solvent is a mixed solvent of toluene and dimethylformamide, the chiral plasmonic hybrid structure may be formed in a rod shape.

[0060] In one embodiment of the present invention, in (ii), the toluene and the dimethylformamide may be mixed in a volume ratio of about 3:1 to about 5:1, or about 4:1.

[0061] In one embodiment of the present invention, the first solution and the second solution may be mixed in a volume ratio of about 0.5:20 to about 3:20 (first solution: second solution).

[0062] In one embodiment of the present disclosure, the heat treatment may be performed at a temperature range of about 40°C to about 90°C, but may not be limited thereto. In one embodiment of the present disclosure, the heat treatment may be performed at a temperature range of about 40°C to about 90°C, about 40°C to about 80°C, about 50°C to about 90°C, or about 50°C to about 80°C, but may not be limited thereto. In one embodiment of the present disclosure, when the first solvent is dimethylformamide alone, the heat treatment may be performed at about 60°C. In one embodiment of the present disclosure, when the first solvent is a mixed solvent of toluene and dimethylformamide, the heat treatment may be performed at about 70°C.

[0063] In one embodiment of the present invention, the heat treatment may be performed for more than 0 hours to about 48 hours, but may not be limited thereto. In one embodiment of the present invention, the heat treatment may be performed for more than 0 hours to about 48 hours, more than 0 hours to about 42 hours, more than 0 hours to about 36 hours, or more than 0 hours to about 30 hours, but may not be limited thereto.

[0064] In one embodiment of the present invention, (i) when the first solvent is dimethylformamide alone, the heat treatment may be performed for about 12 hours to about 48 hours, about 12 hours to about 36 hours, about 18 hours to about 30 hours, or about 24 hours.

[0065] In one embodiment of the present invention, (ii) when the first solvent is a mixed solvent of toluene and dimethylformamide, the heat treatment may be performed for about 30 minutes to about 2 hours, or about 1 hour.

[0066] The third aspect of the present invention provides a material comprising a chiral plasmonic hybrid structure according to the first aspect and applicable to a device.

[0067] Detailed descriptions of overlapping parts with the first and second aspects of the present application have been omitted, but the contents described for the first and second aspects of the present application may be equally applied even if the description is omitted in the third aspect of the present application.

[0068] In one embodiment of the present invention, the device may include a circular polarization detection device, an anti-counterfeiting system, a circular polarization filter, and a display.

[0069] Hereinafter, the present invention will be described in more detail using examples. However, the following examples are provided only to help understand the present invention, and the contents of the present invention are not limited to the following examples.

[0070] [Example]

[0071] A first solution was prepared by adding star-shaped poly(acrylic acid)-block-polystyrene (PAA-b-PS) (5 mg) and R / S-mandelic acid to 1 mL of a solvent and stirring vigorously at room temperature for 2 days. At this time, the molar ratio of acrylic acid monomer and mandelic acid was maintained at 1:2. Dimethylformamide (DMF) and a mixed solvent of toluene and DMF (volume ratio 4:1) were used as the solvent, respectively.

[0072] Star-shaped PAA-b-PS (3 mg) was added to 1 mL of a 1:9 volume ratio mixture of benzyl alcohol and DMF, stirred at room temperature for one day, and then gold precursor (HAuCl4) was added and stirred at room temperature for more than 3 days. Afterwards, a small amount of NaBH4 (reducing agent) dissolved in DMF was added and sufficiently reacted. The molar numbers of AA monomer, gold, and reducing agent were all the same. Afterwards, the concentration was centrifuged to 7.5 mg mL. -1 The second solution was prepared by concentrating it.

[0073] 10 μL of the second solution was mixed with 0.2 mL of the first solution, and then uniformly applied (drop-cast) to a substrate, followed by heat treatment to obtain a chiral plasmonic hybrid structure with gold nanoparticles embedded therein based on supramolecular chiral co-assembly. When DMF solvent was used, heat treatment was performed at 60°C for 24 hours, and when a mixed solvent of toluene and DMF was used, heat treatment was performed at 70°C for 1 hour.

[0074] [Experimental Example]

[0075] Referring to Fig. 2, it was confirmed that gold nanoparticles with an average diameter of 8 nm were synthesized in the star-shaped block copolymer. Referring to Fig. 3, an absorption peak corresponding to localized surface plasmon resonance was observed at 530 nm. Referring to Fig. 4, peaks in X-ray diffraction appeared around 38 degrees and 44 degrees, which are diffraction peaks due to the (111) and (200) crystal planes of the gold nanoparticles.

[0076] <Chiral plasmonic hybrid structure in fiber form>

[0077] Referring to Fig. 5, supramolecular chirality was observed due to strong noncovalent interactions between the block copolymer (PAA-b-PS) and the chiral additive (R / S-mandelic acid) in the 200 nm to 300 nm range. Mirror-symmetric circular dichroism signals appeared in a broad visible wavelength range corresponding to the localized surface plasmon resonance of gold nanoparticles, indicating the formation of a chiral plasmonic hybrid structure. The asymmetry factor was measured to be -0.27 for R-MA and +0.27 for S-MA at 500 nm (Fig. 6).

[0078] Referring to Figure 7, a micro-sized (μm) fiber-like structure was observed consisting of a star-shaped block copolymer hydrogen-bonded with R / S-mandelic acid and gold nanoparticles formed within the star-shaped block copolymer. The gold nanoparticles were embedded in the fiber-like structure.

[0079] Referring to Fig. 8, the X-ray diffraction peaks appearing around 38 degrees and 44 degrees in the chiral plasmonic hybrid structure are diffraction peaks due to the (111) and (200) crystal planes of the gold nanoparticles, proving that the gold nanoparticles are stably embedded within the structure. The diffraction peak around 23 degrees matches the diffraction peak of R / S mandelic acid (R / S-MA), and the diffraction peak around 5.6 degrees matches the diffraction peak of the star-shaped block copolymer (PAA-b-PS, BCP).

[0080] Rod-shaped chiral plasmonic hybrid structure

[0081] Referring to Fig. 9, supramolecular chirality was observed due to strong noncovalent interactions between the block copolymer (PAA-b-PS) and the chiral additive (R / S-mandelic acid) in the 200 nm to 300 nm range. Mirror-symmetric circular dichroism signals appeared in a wide visible wavelength range corresponding to the localized surface plasmon resonance of gold nanoparticles, indicating the formation of a chiral plasmonic hybrid structure. The asymmetry factors were -0.2 (R-MA) and +0.14 (S-MA) at 500 nm (Fig. 10).

[0082] Referring to Figure 11, rod-like structures in the micro (μm) unit were observed, which were composed of a star-shaped block copolymer hydrogen-bonded with R / S-mandelic acid and gold nanoparticles formed within the star-shaped block copolymer, and the rod-like structures were aligned somewhat unevenly and a wrinkled surface was observed.

[0083] Referring to Fig. 12, the X-ray diffraction peaks appearing around 38 degrees and 44 degrees in the chiral plasmonic hybrid structure are diffraction peaks due to the (111) and (200) crystal planes of the gold nanoparticles, proving that the gold nanoparticles are stably embedded within the structure. The diffraction peak around 23 degrees matches the diffraction peak of R / S mandelic acid (R / S-MA), and the diffraction peak around 5.6 degrees matches the diffraction peak of the star-shaped block copolymer (PAA-b-PS, BCP).

[0084] [Comparative example]

[0085] The structure and chirality of chiral plasmonic hybrid structures prepared using linear block copolymers (PS-b-P4VP) instead of star-shaped nonlinear block copolymers as templates for synthesizing gold nanoparticles were analyzed.

[0086] Referring to Figures 13 and 14, a mirror-symmetric circular dichroism signal appears near the local surface plasmon resonance (~500 nm) of the gold nanoparticles, indicating the formation of a chiral supramolecular plasmonic hybrid structure. When gold nanoparticles synthesized based on a linear block copolymer (PS-b-P4VP) template were introduced into the chiral co-assembly, it was confirmed that a chiral supramolecular plasmonic hybrid structure was also formed. However, it was confirmed that the chiral optical properties were deteriorated compared to when a star-shaped nonlinear block copolymer was used, confirming that the synthetic method of this example is a generalizable strategy that is not limited to a specific block copolymer.

[0087] Referring to Figure 15, when a linear block copolymer (PS-b-P4VP) template was used, no specific micrometer (μm)-scale structures were formed. Therefore, it can be seen that when a linear block copolymer (PS-b-P4VP) was used as a template for synthesizing gold nanoparticles, chiral co-assembly to form a fiber-like structure did not occur effectively.

[0088] The above description of the present invention is for illustrative purposes only, and those skilled in the art will readily appreciate that the present invention can be readily modified into other specific forms without altering the technical spirit or essential characteristics of the present invention. Therefore, the embodiments described above should be understood as illustrative in all respects and not restrictive. For example, each component described as a single entity may be implemented in a distributed manner, and similarly, components described as distributed may be implemented in a combined manner.

[0089] The scope of the present invention is indicated by the claims described below rather than the detailed description above, and all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts should be interpreted as being included in the scope of the present invention.

Claims

1. An achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; chiral additives; and Chiral plasmonic nanoparticles A chiral plasmonic hybrid structure comprising:

2. In paragraph 1, The above shell block polymer is a hydrophobic polymer, Chiral plasmonic hybrid structures.

3. In paragraph 2, The hydrophobic polymer comprises at least one selected from polystyrene, polyethylene, polypropylene, polybutadiene, polyaniline, polythiophene, poly(phenylene vinylene), and derivatives thereof. Chiral plasmonic hybrid structures.

4. In paragraph 1, The chiral additive comprises at least one selected from mandelic acid, tartaric acid, aspartic acid, tyrosine, ibuprofen, and hydroxymandelic acid. Chiral plasmonic hybrid structures.

5. In paragraph 1, The above achiral star-shaped block copolymer has a star-shaped structure including multiple arms extending from the core block polymer. Chiral plasmonic hybrid structures.

6. In paragraph 1, The volume ratio of the core block polymer and the shell block polymer is 1:1 to 1:

4. Chiral plasmonic hybrid structures.

7. In paragraph 1, The above chiral plasmonic nanoparticles include at least one selected from Au, Ag, Pt, Pd, Rh, Cu, Al, Mg, In, Ga, and Ni. Chiral plasmonic hybrid structures.

8. In paragraph 1, The diameter of the above chiral plasmonic nanoparticles is 4 nm to 20 nm, Chiral plasmonic hybrid structures.

9. In paragraph 1, The above chiral plasmonic hybrid structure is in the form of a fiber or a rod. Chiral plasmonic hybrid structures.

10. Preparing a first solution by adding an achiral star block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; and a chiral additive to a first solvent; Preparing a second solution by adding an achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer, a reducing agent, and a gold precursor to a second solvent; and Obtaining a chiral plasmonic hybrid structure by mixing and heat-treating the first solution and the second solution. A method for manufacturing a chiral plasmonic hybrid structure, comprising:

11. In paragraph 10, The above chiral plasmonic hybrid structure has a fiber shape or a rod shape depending on the type of the first solvent. Method for fabricating chiral plasmonic hybrid structures.

12. In paragraph 10, The molar ratio of the acrylic acid repeating unit of the polyacrylic acid and the chiral additive is 1:1 to 1:

3. Method for fabricating chiral plasmonic hybrid structures.

13. In paragraph 10, The first solvent comprises at least one selected from dimethylformamide, toluene, tetrahydrofuran, ethyl acetate, 1,4-dioxane, dimethyl sulfoxide, acetonitrile, acetone, ethanol, and methanol. Method for fabricating chiral plasmonic hybrid structures.

14. In paragraph 13, (i) When the first solvent is dimethylformamide alone, the chiral plasmonic hybrid structure is formed in a fiber form, (ii) When the first solvent is a mixed solvent of toluene and dimethylformamide, the chiral plasmonic hybrid structure is formed in a rod shape. Method for fabricating chiral plasmonic hybrid structures.

15. In paragraph 14, (ii), wherein the toluene and the dimethylformamide are mixed in a volume ratio of 3:1 to 5:

1. Method for fabricating chiral plasmonic hybrid structures.

16. In paragraph 10, The first solution and the second solution are mixed in a volume ratio of 0.5:20 to 3:20 (first solution: second solution). Method for fabricating chiral plasmonic hybrid structures.

17. In paragraph 10, The above heat treatment is performed at a temperature range of 40°C to 90°C. Method for fabricating chiral plasmonic hybrid structures.

18. In paragraph 10, The above heat treatment is performed for 0 to 48 hours, Method for fabricating chiral plasmonic hybrid structures.

19. A chiral plasmonic hybrid structure according to paragraph 1, Applicable to the device, subject matter.

20. In paragraph 19, The material comprises a circular polarization detection element, an anti-counterfeiting system, a circular polarization filter, and a display.

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