Metallo-Dielectric Photonic Crystals for Surface-Enhanced Raman Scattering

Zhao, Yu; Zhang, Xue Jin; Ye, Jing; Chen, Li Miao; Lau, Shu Ping; Zhang, Wenjun; Lee, Shuit Tong

doi:10.1021/nn2001068

Cited by 47 publications

(32 citation statements)

References 45 publications

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“…However, the drawbacks of PVD as mentioned above would inhibit a full utilization of original biotemplates’ 3D morphologies. In comparison, using the unique metallic structures (or “chemical scales”) synthesized with the chemical approach reported herein as SERS substrates, the detectable lower limit of analyte concentration can surprisingly decrease by even one order of magnitude (Rhodamine 6G, 10 −13 M ), as compared with commercial substrates (10 −12 M , Klarite, Renishaw Diagnostics), and with studies published very recently 16a–c. Moreover, the lowest detectable R6G concentration on chemical scales drastically decreases by four orders of magnitude as compared with the use of Au scales that were prepared by simple physical deposition (physical scales) 3d.…”

supporting

confidence: 63%

Versatile Fabrication of Intact Three‐Dimensional Metallic Butterfly Wing Scales with Hierarchical Sub‐micrometer Structures

Tan

Zang

et al. 2011

Angewandte Chemie

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Three-dimensional (3D) metallic microstructures with wellcontrolled hierarchical morphologies down to the sub-micrometer scale have attracted considerable attention. [1] These structures have broad applications owing to their unique optical, [2a] electronic, [2b] magnetic, [2c] thermal, [2d,e] and catalytic [2f] properties, which can be modulated by their intrinsic microstructures. Such structures, however, are quite difficult to prepare by traditional methods. One promising route to create these metallic structures is direct replication from hierarchical structures of various natural species. Metals have been physically deposited onto biological structures to fabricate metallic structures through physical vapor deposition (PVD). [3] However, the line-of-sight nature of PVD prevented a complete replication of the biotemplates original 3D morphologies. [4] Some groups elegantly converted natural inorganic structures such as diatom frustules into metals (Ag, Au, Pd) using wet-chemical processes, [4] but many natural species with functional structures are composed of organic materials. Versatile synthesis of metallic structures using organic-based natural species intact, 3D, and hierarchical sub-micrometer morphologies as templates is thus needed.Herein we present a versatile route (selective surface functionalization and subsequent electroless deposition) to generate metallic replicas of the intact 3D organic butterfly (Euploea mulciber) wing scales. This method can replicate the original chitin-based scales morphology in at least seven important metals, including cobalt, nickel, copper, palladium, silver, platinum, and gold ( Figure 1 and Figure 2). Significantly, using the synthetic Au scale as a surface-enhanced Raman scattering (SERS) substrate, the detectable analyte concentration (Rhodamine 6G, 10 À13 m) can be one order of magnitude lower than using commercial substrates (Klarite). To our knowledge, this work is the first demonstration of the conversion of intact hierarchical 3D butterfly structures on a sub-micrometer level into metallic replicas. It should be noted that butterflies belong to the order Lepidoptera (Latin word for "scaly wing", including butterflies and moths) that comprises an estimated 174 250 species. [5] A given species usually has more than one type of wing scale, [6] and such huge morphological diversity offers a vast structure pool for biotemplate selection (e.g., photonic crystal design). [7a] In addition, chitin, the main component of butterfly wing scales, is one of the richest natural macromolecular compounds. [8] Therefore, this approach can be extended to replicate other chitin-based biostructures, including fungi cell walls, exoskeletons of insects [9a,b] and arthropods (e.g., crabs and lobsters), [9c] radulas of mollusks (e.g., snails), and beaks of cephalopods (e.g., squids [9d] and octopuses). The fabrication route described herein consists of three steps (see Scheme S1 in the Supporting Information): 1) func- Figure 1. SEM element mapping images of seven meta...

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supporting

confidence: 63%

Versatile Fabrication of Intact Three‐Dimensional Metallic Butterfly Wing Scales with Hierarchical Sub‐micrometer Structures

Tan

Zang

et al. 2011

Angewandte Chemie

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“…These results are comparable with those of many other hierarchical plasmonic substrates. 9,24,43 More importantly, the mechanism presented here can act as a guideline for the future design and selection of SPR substrates. The existence of several other bicontinuous interconnected structures has been confirmed in various biological systems and self-assembly systems, such as the diamond structure found in the brilliantly green weevil Lamprocyphus augustus 25 and the double-gyroid, 44 stripedgyroid 26 and double-diamond 45 structures in block polymer systems.…”

Section: Surface-enhanced Raman Spectroscopy L Wu Et Almentioning

confidence: 97%

“…These results are comparable to those of many other SPR substrates, whereas the detection concentration is one or two orders of magnitude lower. 24,43 Meanwhile, to investigate the influence of the randomly oriented distribution of domains on the uniformity of SPR enhancement by the GAPMMs, a point-by-point SERS mapping measurement was conducted on a 20 μm × 20 μm area in zone A for the detection of CV (10 − 10 M). The step lengths in both the X and Y directions were 1 μm.…”

Section: Surface-enhanced Raman Spectroscopy L Wu Et Almentioning

confidence: 99%

Highly sensitive, reproducible and uniform SERS substrates with a high density of three-dimensionally distributed hotspots: gyroid-structured Au periodic metallic materials

Wang

Zhang

et al. 2018

NPG Asia Mater

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Surface-enhanced Raman spectroscopy (SERS) is an important tool for the analytical, trace detection of many inorganic and organic materials, especially for materials involved in medical care, food safety and environmental pollution. Numerous efforts have been dedicated to exploring periodic metallic materials with a high density of hotspots. However, for most periodic metallic materials fabricated by top-down and bottom-up approaches, the distribution of hotspots is restricted to one or two dimensions. Here, for the first time, we report the successful fabrication of a bio-inspired bicontinuous gyroid-structured Au SERS substrate with a high density of three-dimensionally (3D) distributed hotspots. The as-required gyroid-structured substrates were demonstrated to be highly sensitive, reproducible and uniform, with an enhancement factor of up to 10 9 . Finite-difference time domain (FDTD) simulations were conducted to reveal the mechanism leading to the high enhancement and we found that the interconnected helices in the gyroid structure not only increase the hotspot density but also contribute to increasing the scattering cross-section of the incident laser. The substrate was then adopted for the SERS detection of bis(2-ethylhexyl) phthalate, the most frequently used plasticizer in food, paints, house-hold items, perfumes and so on, and reached a detection limit of 1 fM, which is among the best results ever reported. Moreover, the mechanism deduced here will provide insight into the future design and selection of novel surface plasmonic resonance substrates, as many other bicontinuous interconnected systems are available. NPG Asia Materials (2018) 10, e462; doi:10.1038/am.2017.230; published online 12 January 2018 INTRODUCTIONThe fabrication of surface plasmonic resonance (SPR) materials with ultra-high plasmonic enhancement has long been a critical research area due to their broad applications as chemical sensors, biological sensors, plasmonic solar cells, photocatalysts and other environmentally friendly devices. 1-3 Among these applications, the most famous is the surface-enhanced Raman spectroscopy (SERS) detection of trace analytes, especially for analytes involved in medical care, food safety and environmental pollution. Various nanoparticle systems with novel nanomorphologies and their assemblies have been fabricated and reported to show excellent SPR performance. 2-5 However, SERS nanostructures composed of nanoparticles face significant challenges in achieving a reproducible and uniform Raman response due to the difficulty in fabricating uniform SERS active sites. Periodic metallic materials could provide hotspots with high density, reproducibility and uniformity, which completely meet the requirement of valid SERS substrates, and therefore numerous efforts have been dedicated to engineering periodic metallic materials with novel nanomorphologies,

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confidence: 99%

Silver‐Coated Rose Petal: Green, Facile, Low‐Cost and Sustainable Fabrication of a SERS Substrate with Unique Superhydrophobicity and High Efficiency

Zhang

et al. 2013

Advanced Optical Materials

107

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56 wileyonlinelibrary.com COMMUNICATION www.MaterialsViews.com www.advopticalmat.deRecent years have witnessed a rapidly increased research interest in surface enhanced Raman scattering (SERS) spectroscopy, [1][2][3][4][5][6] because the surface-sensitive technique, so-called SERS, can directly provide the fi ngerprint information of various target molecules, and thus allows highly sensitive detection of analytes at very low concentration, [ 7 ] even single molecule level. To date, despite a short history, SERS has already revealed a cornucopia of both new photo-physics and practical applications in various chemical [ 8,9 ] and biological analyses. [ 6,10 ] In principle, the signifi cantly enhanced Raman scattering of target molecules could be mainly attributed to the enhanced E-fi elds in the vicinity of plasmonic structures, as high as a factor of E 4 . [ 11 ] Consequently, great efforts have been devoted to the fabrication of metal-based hierarchical nanostructures that can focus light into nanosized volumes [ 12 ] and form a localized surface plasmon resonance (LSPR) mode for the purpose of increasing the E-fi eld. [ 13,14 ] To some extent, the preparation of SERS substrate shows certain dependence on the state-of-the-art of micronanofabrication techniques. [ 15 ] Despite the fact that various "top-down" and "bottom-up" approaches [ 16 ] represented by lithography, [ 17 , 18 ] nanoimprinting, [ 19 ] self-assembly [ 20 ] and laser direct writing [ 21,23 ] have been successfully adopted for the fabrication of periodic or rough metal nanostructures for SERS enhancement, the complexity, harsh experimental conditions and high-cost of the preparative procedures signifi cantly limit their wide applications in various routine analysis, making the SERS detection an "in-lab-only" technique. In this regard, to achieve SERSactive substrates with nanostructure-defi ned LSPR in a green, facile, low cost and sustainable manner is highly desired, but obviously, it remains a scientifi c challenge.On the other hand, in order to further lower the SERS detection limit, superhydrophobic surfaces have been recently adopted for the enrichment of the low-concentration analytes. [24][25][26] For instance, F. Gentile et al. [ 25 ] fi rstly reported the SERS signal of Rhodamine 6G (R6G) with an ultra-low concentration of 10 −18 M by using superhydrophobic substrate comprising a regular lattice of silicon micro-pillar arrays covered with silver nanograin aggregates. The greatly reduced contact area between analyte solution and SERS substrate would significantly enrich the target molecules and further lower the detection limit. Besides, Z. Li et al. [ 26 ] modifi ed silver nanoparticle coated zinc oxide nanorod arrays with stearic acid and gained one order of magnitude of detection limit less than that of hydrophilic ones, confi rming the contribution of superhydrophobicity to SERS detection.It is well known that natural creatures usually possess superhydrophobicity due to the presence of almost perfect micronanostructures in a wide sca...

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Metallo-Dielectric Photonic Crystals for Surface-Enhanced Raman Scattering

Cited by 47 publications

References 45 publications

Versatile Fabrication of Intact Three‐Dimensional Metallic Butterfly Wing Scales with Hierarchical Sub‐micrometer Structures

Versatile Fabrication of Intact Three‐Dimensional Metallic Butterfly Wing Scales with Hierarchical Sub‐micrometer Structures

Highly sensitive, reproducible and uniform SERS substrates with a high density of three-dimensionally distributed hotspots: gyroid-structured Au periodic metallic materials

Silver‐Coated Rose Petal: Green, Facile, Low‐Cost and Sustainable Fabrication of a SERS Substrate with Unique Superhydrophobicity and High Efficiency

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