KR-102963647-B1 - CHIRAL PLASMONIC HYBRID STRUCTURE AND METHOD OF PREPARING THE SAME

Abstract

The present invention relates to a chiral plasmonic hybrid structure and a method for manufacturing the same. The chiral plasmonic hybrid structure according to the embodiments of the present invention possesses excellent chiral optical properties and can be applied as a promising material in next-generation applications such as circular polarization sensing devices, anti-counterfeiting systems, circular polarization filters, and displays.

Inventors

• 김동하
• 김민주
• 정서현

Assignees

• 이화여자대학교 산학협력단

Dates

Publication Date

20260511

Application Date

20240327

Claims (20)

1. A achiral star-shaped block copolymer comprising polyacrylic acid as a core block polymer and a shell block polymer; Chiral additives; and Chiral plasmonic nanoparticles As a chiral plasmonic hybrid structure comprising, The above-mentioned achiral star-shaped block copolymer is a star-shaped structure comprising a plurality of arms extending from the core block polymer, and The above chiral plasmonic nanoparticles comprise one or more selected from Au, Ag, Pt, Pd, Rh, Cu, Al, Mg, In, Ga, and Ni, and The chiral plasmonic hybrid structure is formed by the co-assembly of the achiral star-shaped block copolymer hydrogen-bonded with the chiral additive and the achiral star-shaped block copolymer containing the chiral plasmonic nanoparticles. Chiral plasmonic hybrid structure.
2. In Article 1, The above shell block polymer is a hydrophobic polymer, Chiral plasmonic hybrid structure.
3. In Article 2, The above hydrophobic polymer comprises one or more selected from polystyrene, polyethylene, polypropylene, polybutadiene, polyaniline, polythiophene, poly(phenylene vinylene), and derivatives thereof. Chiral plasmonic hybrid structure.
4. In Article 1, The chiral additive comprises one or more selected from mandelic acid, tartaric acid, aspartic acid, tyrosine, ibuprofen, and hydroxymandelic acid. Chiral plasmonic hybrid structure.
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6. In Article 1, The volume ratio of the core block polymer and the shell block polymer is 1:1 to 1:4. Chiral plasmonic hybrid structure.
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8. In Article 1, The diameter of the chiral plasmonic nanoparticles is 4 nm to 20 nm. Chiral plasmonic hybrid structure.
9. In Article 1, The above chiral plasmonic hybrid structure is in the form of fibers or rods, Chiral plasmonic hybrid structure.
10. An achiral star-shaped block copolymer comprising polyacrylic acid and a shell block polymer as a core block polymer; and preparing a first solution by adding a chiral additive to a first solvent; Preparing a second solution by adding an achiral star-shaped block copolymer comprising polyacrylic acid and a shell block polymer as core block polymers, a reducing agent, and a gold precursor to a second solvent; and A chiral plasmonic hybrid structure obtained by mixing and heat-treating the first solution and the second solution. A method for manufacturing a chiral plasmonic hybrid structure according to claim 1, comprising
11. In Article 10, The chiral plasmonic hybrid structure has a fiber form or a rod form depending on the type of the first solvent. Method for manufacturing a chiral plasmonic hybrid structure.
12. In Article 10, The molar ratio of the acrylic acid repeating unit of the polyacrylic acid to the chiral additive is 1:1 to 1:3. Method for manufacturing a chiral plasmonic hybrid structure.
13. In Article 10, The first solvent comprises one or more selected from dimethylformamide, toluene, tetrahydrofuran, ethyl acetate, 1,4-dioxane, dimethyl sulfoxide, acetonitrile, acetone, ethanol, and methanol. Method for manufacturing a chiral plasmonic hybrid structure.
14. In Article 13, (i) When the first solvent is dimethylformamide alone, the chiral plasmonic hybrid structure is formed in the form of fibers, and (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 manufacturing a chiral plasmonic hybrid structure.
15. In Article 14, (ii) wherein the toluene and the dimethylformamide are mixed in a volume ratio of 3:1 to 5:1, Method for manufacturing a chiral plasmonic hybrid structure.
16. In Article 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 manufacturing a chiral plasmonic hybrid structure.
17. In Article 10, The above heat treatment is performed in a temperature range of 40℃ to 90℃, Method for manufacturing a chiral plasmonic hybrid structure.
18. In Article 10, The above heat treatment is performed for more than 0 hours to 48 hours, Method for manufacturing a chiral plasmonic hybrid structure.
19. A material comprising a chiral plasmonic hybrid structure according to claim 1, It is applicable to devices, and The above-mentioned element is a material comprising a circularly polarized light sensing element, an anti-counterfeiting system, a circularly polarized light filter, and a display.
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Description

Chiral Plasmonic Hybrid Structure and Method of Preparing the Same The present invention relates to a chiral plasmonic hybrid structure and a method for manufacturing the same. The field of chiral materials has grown significantly, inspired by the abundant chiral structures found in nature. Among these, chiral supramolecular assembly has garnered considerable attention due to the complexity and diversity of its structural and chiroptical properties. Such assembly derives supramolecular chirality from the asymmetric arrangement of constituent molecules through non-covalent bonds that act as a bridge 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. The generation of supramolecular chirality can be manipulated by carefully controlling various variables. The kinetics and thermodynamics of chiral supramolecular assembly can be controlled by carefully designing the molecular structure of building blocks or by controlling dynamic non-covalent interactions, solvent effects, stoichiometry, temperature, and time. This has led to the generation 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 has presented exciting prospects for the development of advanced materials and functional systems with intriguing properties and applications across various research fields. Plasmonic properties refer to strong light-matter interactions in which nanometer-sized metal particles interact with light through localized surface plasmon resonance to produce enhanced optical phenomena. Representative fabrication methods for chiral plasmonic structures, which are metal structures integrating these plasmonic properties and chirality, include transferring the chirality of chiral molecules to plasmonic structures using chiral surface ligands; vapor deposition methods such as physical vapor deposition (top-down approach); and asymmetric alignment of chiral nanoparticles using chiral templates (bottom-up approach). These synthesis methods are simple and effective ways to create chiral plasmonic hybrid structures with diverse configurations and structures. Although supramolecular assembly frameworks can induce various chiral arrangements or configurations of achiral nanostructures (Ag or Au NPs), the presence of weak chiral optical activity, ineffective evolution of plasmonic chirality, and structural instability currently limits their application in various important fields such as catalysis, sensing, and optics. FIG. 1 is a schematic diagram of a method for manufacturing a chiral plasmonic hybrid structure according to one embodiment of the present invention. FIG. 2 is a transmission electron microscope (TEM) image of a star-shaped block copolymer template synthesized with gold nanoparticles in one embodiment of the present invention. FIG. 3 is the absorption spectrum of a star-shaped block copolymer template synthesized with gold nanoparticles in one embodiment of the present invention. FIG. 4 is an X-ray diffraction graph of a star-shaped block copolymer template synthesized with gold nanoparticles in one embodiment of the present invention. FIG. 5 is the circular dichroism and absorption spectrum 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. FIG. 6 is an asymmetry factor graph of a fiber-shaped chiral plasmonic hybrid structure in one embodiment of the present invention. 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. FIG. 8a and b are X-ray diffraction graphs for a fiber-shaped chiral plasmonic hybrid structure and each co-assembled component in one embodiment of the present invention. FIG. 9 is the circular dichroism and absorption spectrum 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. FIG. 10 is an asymmetry factor graph of a rod-shaped chiral plasmonic hybrid structure in one embodiment of the present invention. Figures 11a to 11d are SEM images of a rod-shaped chiral plasmonic hybrid structure in one embodiment of the present invention. FIG. 12 is an X-ray diffraction graph of a rod-shaped chiral plasmonic hybrid structure in one embodiment of the present invention. FIG. 13 is the circular dichroism and absorption spectrum of a chiral