DOI QR코드

DOI QR Code

The Study of Surface Plasmonic Bands Using Block Copolymer Nanopatterns

블록공중합체 나노패턴을 이용한 표면 플라즈몬 연구

  • 유승민 (울산과학대학교 환경화학공업과)
  • Received : 2017.08.21
  • Accepted : 2017.11.03
  • Published : 2017.11.30

Abstract

It is important to develop a simple method oftuning localized surface plasmon resonance(LSPR) properties, due to their numerous applications. In addition, the careful examination of the shape, size and combination of metal nanoparticles is useful for understanding the relation between the LSPR properties and metal nanostructures. This article describes the dependence of theLSPR properties on the arrays of metal nanoparticles obtained from a block copolymer(BCP) micellar thin film. Firstly, two different Au nanostructures, having a dot and ring shape, were fabricated using conventional block copolymer micelle lithography. Then, Ag was plated on the Au nanostructures through the silver mirror reaction technique to obtain Au/Ag bimetallic nanostructures. During the production of these metallic nanostructures, the processing factors, such as the pre-treatment by ethanol, silver mirror reaction time and removal or not of the BCP, were varied. Once the Au nanoparticles were synthesized, Ag was properly plated on the Au, providing two distinguishable characteristic plasmonic bands at around 525nm for Au and around 420nm for Ag, as confirmed bythe UV-vis measurements. However, when a small amount of Au seed nanoparticles, which accelerate the Ag plating speed,was formed by usinga block copolymer with a relatively highmolecular weight, all of the Au surfaces were fully covered by Ag during the silver mirror reaction, showing only the characteristic peak for Ag at around 420nm. The Ag plating technique on Au nanoparticles pre-synthesized from a block copolymer is useful to study the LSPR properties carefully.

다양한 응용분야를 가진 국부적인 표면플라즈몬 공명 특성을 손쉽게 제어할 수 있는 기술 개발은 매우 중요하다. 또한, 금속 나노입자의 형태, 크기, 그리고 조합에 관한 세심한 조사는 공명특성과 금속 나노구조의 관계를 이해하는데 매우 유용하다. 본 논문은 블록공중합체 마이셀 박막필름으로부터 얻어진 금속나노입자 배열에 따른 국부적인 표면플라즈몬의 공명특성에 관한 연구이다. 우선 전통적인 방법의 블록공중합체 리소그라피를 통해 두 가지 다른, 점 형태 및 링 형태, 금 나노입자를 제조하였다. 그 다음 은거울 반응을 통하여 금 나노입자위에 은이 둘러 쌓이도록 금/은 이중금속 나노구조를 구현했다. 금속 나노 구조체 조절을 위해 에탄올 전처리, 은거울 반응 시간, 블록공중합체의 제거 유무 등의 공정변수를 변화시켰다. 초기 금 나노입자가 잘 제조된 경우 항상 금나노입자 표면에 적절히 은이 잘 형성되었고, 이는 UV-Vis 실험에서 각 금속나노 입자의 고유 플라즈몬 밴드인 금 525nm, 은 420nm에서 각각 나타났다. 하지만 최초 적은 양의 금 나노입자가 제조되었을 경우 은 도금 속도가 빨라져서, 초기 금 나노입자의 표면을 은이 완전히 덮었으며, 이는 UV-Vis 실험에서 금의 플라즈몬 밴드는 나타나지 않고, 은의 고유 플라즈몬 밴드만 420nm에서 나타났다. 블록공중합체로부터 미리 합성된 금나노입자 위에 은을 도금하는 방법은 국부적인 표면플라즈몬 특성을 면밀히 조사하는데 매우 유용하다.

Keywords

References

  1. Hahn B, Wendorff J, and Yoon DY, "Dielectric relaxation of the crystal-amorphous interphase in poly(vinylidene fluoride) and its blends with poly(methyl methacrylate)", Macromolecules vol. 18, no. 4, pp. 718-721, 1985. DOI: https://doi.org/10.1021/ma00146a024
  2. Liz-Marzan LM, "Tailoring Surface Plasmons through the Morphology and Assembly of Metal Nanoparticles", Langmuir vol. 22, no. 1, pp. 32-41, 2006. DOI: https://doi.org/10.1021/la0513353
  3. Preciado-Flores S, Wang D, Wheeler DA, Newhouse R, Hensel JK, Schwartzberg A, Wang L, Zhu J, Barboza-Florese M, and Zhang JZ, "Highly reproducible synthesis of hollow gold nanospheres with near infrared surface plasmon absorption using PVP as stabilizing agent " J. Mater. Chem. vol. 21, no. 7, pp. 2344-2350, 2011. DOI: https://doi.org/10.1039/C0JM03690K
  4. Aherne D, Ledwith DM, Gara M, and Kelly JM, "Optical properties and growth aspects of silver nanoprisms produced by a highly reproducible and rapid synthesis at room temperature" Adv. Func. Mater. vol. 18, no. 14, pp. 2005-2016, 2008. DOI: https://doi.org/10.1002/adfm.200800233
  5. Kim UJ, Yoo S, Park Y, Shin M, Kim J, Jeong H, Baik CW, Roh YG, Lee J, Im K, Son H, Hwang S, Lee CW, and Park S, "Plasmon-Assisted Designable Multi-Resonance Photodetection by Graphene via Nanopatterning of Block Copolymer" ACS Photonics vol. 2, no. 4, pp. 506-514, 2015. DOI: https://doi.org/10.1021/ph500412p
  6. Rosi NL, Mirkin CA, "Nanostructures in biodiagnostics" Chem. Rev. vol. 105, no. 4, pp. 1547-1562, 2005. DOI: https://doi.org/10.1021/cr030067f
  7. Yoo S, Shin M, Kim UJ, Lee CW, Park S, "Block-Copolymer-Based Au/Ag Nanoring Arrays with Widely Tunable Surface Plasmon Resonance", Sci. of Adv. Mater. vol. 7, no. 5, pp. 842-847, 2015. DOI: https://doi.org/10.1166/sam.2015.1871
  8. Wang Y, Li F, "An Emerging Pore-Making Strategy: Confined Swelling-Induced Pore Generation in Block Copolymer Materials", Adv. Mater vol. 23, no. 19, pp. 2134-2148, 2011. DOI: https://doi.org/10.1002/adma.201004022