Hierarchically Well-Ordered Array of Concentric Silver Nanorings for Highly Sensitive Surface-Enhanced Raman Scattering Substrate

Bae, Dusik; Cho, Won Joon; Jeon, Gumhye; Byun, Jinseok; Kim, Jin Kon

doi:10.1021/jp309008c

Cited by 13 publications

(14 citation statements)

References 50 publications

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“…For the self-assembly of BCPs under confinement, the confining environment plays an important role in determining both shape and internal morphologies of polymeric entities. Additionally, in the case of templates with ordered patterns, hierarchical patterns of BCP microdomains could be obtained, which have potential applications such as photonics and optical materials. − For example, previous studies developed hierarchically ordered concentric silver nanoring arrays for highly sensitive surface-enhanced Raman scattering substrates using BCPs confined in ordered cavities. Even though hierarchically ordered nanopatterns in two dimension have been studied, the development of fabrication routes for hierarchical three-dimensional (3D) nanostructures with controllable nanosized domains still remains a challenge.…”

Section: Introductionmentioning

confidence: 99%

Self-Assembled Morphologies of Lamella-Forming Block Copolymers Confined in Conical Nanopores

Kim

Kumagai

et al. 2019

Macromolecules

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Block copolymers (BCPs) under nanoscale confinement can self-assemble to form novel nanostructures that are not available in the bulk state. Particularly, the ordering process of block copolymers and the resulting morphologies depend sensitively on the dimensionality, geometry, and surface property of the confining environment. In this study, we report on the self-assembled morphologies of polystyrene-block-1,4-polybutadiene (PS-b-PB) confined in conical pores of various sizes, shapes, and surface properties. Based on the experimental observations from transmission electron microscopy and theoretical calculation using the simulated annealing method, we found that the phase separation of PS-b-PB under the conical confinement is competitively determined by three thermodynamic factors: (1) the interfacial energy between two blocks, (2) the surface energy between the blocks and the surrounding environment (i.e., air and substrates), and (3) the entropic penalty associated with the large curvature at the vertices of conical pores. In addition, three-dimensional imaging of transmission electron microtomography was also performed in an attempt to gain more detailed information on the internal nanostructures of the BCP.

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Section: Introductionmentioning

confidence: 99%

Self-Assembled Morphologies of Lamella-Forming Block Copolymers Confined in Conical Nanopores

Kim

Kumagai

et al. 2019

Macromolecules

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“…4−10 In addition, concentric nanopatterns with sub-5 nm periodicity for use as templates for nanostructured noble metals have the potential to dramatically increase surface-enhanced Raman scattering. 11,12 The concentric nanopatterns are reported to be used as a template for nanostructured metals applicable to a microzone plate in soft Xray microscopy. 13,14 Self-assembled block copolymers are known to bend along the curved surfaces of spheres, 15,16 and the surrounding nanostructures are expected to be elastically deformed to form concentric structures in the same way that the orientation directions of liquid crystals are distorted by spheres.…”

Section: ■ Introductionmentioning

confidence: 99%

Formation of Concentric Silica Nanogrooves Guided by the Curved Surface of Silica Particles

Hara¹,

Hirota²,

Tabe

et al. 2018

Langmuir

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The flexible control of nanopatterns by a bottom-up process at the nanometer scale is essential for nanofabrication with a finer pitch. We have previously reported that for the fabrication of linear nanopatterns with sub-5 nm periodicity on Si substrates the outermost surfaces of assembled micelles facing the substrates can be replicated with soluble silicate species generated from the Si substrates under basic conditions. In this study, concentrically arranged nanogrooves with a sub-5 nm periodicity were prepared on Si substrates by replicating the outermost surfaces of bent micelles guided by silica particles. The Si substrates, where silica particles and surfactants films were deposited, were exposed to an NH-water vapor mixture. During the vapor treatment, cylindrical micelles became arranged in concentric patterns centered on the silica particles, and their outermost surfaces facing the substrates were replicated by soluble silicate species on the Si substrates. The thinness of the surfactant film on the substrate is crucial for the formation of concentric silica nanogrooves because the out-of-plane orientations of the micelles are suppressed at the interface. Surprisingly, the domains of the concentric silica nanogrooves spread to much larger areas than the maximum cross-sectional areas of the particles, and the size of the domains increased linearly with the radii of the particles. The extension of concentric nanogrooves is discussed on the basis of the orientational elastic energies of the micelles around one silica particle. This study of the formation of bent nanogrooves guided by the outlines of readily deposited nanoscale objects provides a new nanostructure-guiding process.

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“…6,7 Several attempts have been made to increase the sensitivity and reproducibility for active SERS substrates. Two-dimensional arrays of various SERS-active substrates were introduced 8,9 but were not suitable for detection in solution or in an in vivo system because of the use of solid substrates. 10,11 To directly detect target molecules in a solution, colloidal three-dimensional (3D) SERS-active particles that could be easily dispersed in an environmental matrix, such as water, are strongly needed for label-free immunoassays and on-time biosensors.…”

Section: Introductionmentioning

confidence: 99%

Plasmonic colloidal nanoparticles with open eccentric cavities via acid-induced chemical transformation

et al. 2015

Self Cite

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Surface-enhanced Raman spectroscopy (SERS) has been considered a promising technique for the detection of trace molecules in biomedicine and environmental monitoring. The ideal metal nanoparticles for SERS must not only fulfill important requirements such as high near-field enhancement and a tunable far-field response but also overcome the diffusion limitation at extremely lower concentrations of a target material. Here, we introduce a novel method to produce gold nanoparticles with open eccentric cavities by selectively adapting the structure of non-plasmonic nanoparticles via acid-mediated surface replacement. Copper oxide nanoparticles with open eccentric cavities are first prepared using a microwave-irradiation-assisted surfactant-free hydrothermal reaction and are then transformed into gold nanoparticles by an acidic gold precursor while maintaining their original structure. Because of the strong near-field enhancement occurring at the mouth of the open cavities and the very rough surfaces resulting from the uniformly covered hyperbranched sharp multi-tips and the free access of SERS molecules inside of the nanoparticles without diffusion limitation, adenine, one of the four bases in DNA, in an extremely diluted aqueous solution (1.0 pM) was successfully detected with excellent reproducibility upon laser excitation with a 785-nm wavelength. The gold nanoparticles with open eccentric cavities provide a powerful platform for the detection of ultra-trace analytes in an aqueous solution within near-infrared wavelengths, which is essential for highly sensitive, reliable and direct in vivo analysis. INTRODUCTIONThere is a strong demand for trace-molecule detection techniques that are simple, rapid, highly sensitive and reproducible, spanning from diagnostics in medicine to the detection of base sequence mutation. Surface-enhanced Raman spectroscopy (SERS) could be a promising candidate for extremely sensitive molecular finger-printing techniques that fulfill these technological and detection system criteria. 1 SERS is a near-field phenomenon that relies on the intensified electric fields (E-fields) on a metal nanostructure when its localized surface plasmon resonance is excited by light. 2 These enhanced E-fields lead to a large enhancement of the Raman scattering signal. 3 Although the hot spots exhibiting these intensively localized E-fields that are usually expected between two (or multiple) noble metal nanoparticles and the sharp nanoscale tips can amplify Raman signals by 410 6 times for trace molecule detection, 4,5 they are not easily obtained. 6,7 Several attempts have been made to increase the sensitivity and reproducibility for active SERS substrates. Two-dimensional arrays of various SERS-active substrates were introduced 8,9 but were not suitable for detection in solution or in an in vivo system because of

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Hierarchically Well-Ordered Array of Concentric Silver Nanorings for Highly Sensitive Surface-Enhanced Raman Scattering Substrate

Cited by 13 publications

References 50 publications

Self-Assembled Morphologies of Lamella-Forming Block Copolymers Confined in Conical Nanopores

Self-Assembled Morphologies of Lamella-Forming Block Copolymers Confined in Conical Nanopores

Formation of Concentric Silica Nanogrooves Guided by the Curved Surface of Silica Particles

Plasmonic colloidal nanoparticles with open eccentric cavities via acid-induced chemical transformation

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