Self‐organized Polymer Wrinkles: A Lithography‐free Pathway for Surface‐enhanced Raman Scattering (SERS) Substrates

Stenberg, H.; Matikainen, Antti; Daniel, Salman; Nuutinen, Tarmo; Stenberg, Pauline; Honkanen, Seppo; Pakkanen, Tuula T.; Vahimaa, Pasi; Suvanto, Mika

doi:10.1002/mame.201400391

Cited by 16 publications

(8 citation statements)

References 12 publications

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“…The surfaces were patterned in order to evoke SERS activity, which was done with the aid of polymer wrinkles (see ref. 20 for further information). Again, for the SERS measurements, the same Rh6G treatment was performed for each sample.…”

Section: Methodsmentioning

confidence: 99%

Atmospheric oxidation and carbon contamination of silver and its effect on surface-enhanced Raman spectroscopy (SERS)

Matikainen

Nuutinen

Itkonen

et al. 2016

Sci Rep

Self Cite

104

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Surface-enhanced Raman spectroscopy (SERS) is considered a highly promising technology for different analytical purposes. The applications of SERS are still quite limited due its relatively poor quantitative repeatability and the fact that SERS is very sensitive to oxidation, which is a challenge especially with silver based SERS substrates. Here, the link between these phenomena is investigated by exposing silver SERS substrates to ambient laboratory air. We show that SERS intensity decreases exponentially after the exposure, which consequently leads to an increasing standard deviation (σ) in intensity. Within a five-hour measurement window, the SERS intensity already drops by 60%, while σ triples from 7% to 21%. The SERS results are supplemented by elemental analysis, which shows that oxidation and atmospheric carbon contamination coincide with the rapid SERS intensity decrease. The results emphasize how sensitive SERS is towards atmospheric contamination and how it can also reduce the measurement repeatability – even if the substrates are exposed to air just for a very short period of time.

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Section: Methodsmentioning

confidence: 99%

Atmospheric oxidation and carbon contamination of silver and its effect on surface-enhanced Raman spectroscopy (SERS)

Matikainen

Nuutinen

Itkonen

et al. 2016

Sci Rep

Self Cite

104

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“…Second, the wrinkling increases the surface area of the polymer and, thus, improves the sample adsorption . The third possible mechanism of enhancement is the intrinsic roughness of the polymer surface . However, this proof-of-concept work evaluating the SERS capabilities of wrinkled PEGDA surfaces should be complemented by future experimentations to explore the influence of various wrinkling characteristics, such as wrinkling wavelength, amplitude, and surface roughness, on the Raman spectroscopy enhancement factor.…”

Section: Resultsmentioning

confidence: 99%

“…31 The third possible mechanism of enhancement is the intrinsic roughness of the polymer surface. 44 However, this proof-ofconcept work evaluating the SERS capabilities of wrinkled PEGDA surfaces should be complemented by future experimentations to explore the influence of various wrinkling characteristics, such as wrinkling wavelength, amplitude, and surface roughness, on the Raman spectroscopy enhancement factor. It is expected that smaller wavelengths and larger amplitudes increase the enhancement factor provided that the aforementioned mechanisms are indeed responsible for the observed SERS effect.…”

Section: ■ Introductionmentioning

confidence: 99%

Plasmon-Free Polymeric Nanowrinkled Substrates for Surface-Enhanced Raman Spectroscopy of Two-Dimensional Materials

et al. 2020

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We report plasmon-free polymeric nanowrinkled substrates for surface-enhanced Raman spectroscopy (SERS). Our simple, rapid, and cost-effective fabrication method involves depositing a poly(ethylene glycol)diacrylate (PEGDA) prepolymer solution droplet on a fully polymerized, flat PEGDA substrate, followed by drying the droplet at room conditions and plasma treatment, which polymerizes the deposited layer. The thin polymer layer buckles under axial stress during plasma treatment due to its different mechanical properties from the underlying soft substrate, creating hierarchical wrinkled patterns. We demonstrate the variation of the wrinkling wavelength with the drying polymer molecular weight and concentration (direct relations are observed). A transition between micron to nanosized wrinkles is observed at 5 v % concentration of the lower molecular-weight polymer solution (PEGDA M n 250). The wrinkled substrates are observed to be reproducible, stable (at room conditions), and, especially, homogeneous at and below the transition regime, where nanowrinkles dominate, making them suitable candidates for SERS. As a proof-of-concept, the enhanced SERS performance of micro/nanowrinkled surfaces in detecting graphene and hexagonal boron nitride (h-BN) is illustrated. Compared to the SiO2/Si surfaces, the wrinkled PEGDA substrates significantly enhanced the signature Raman band intensities of graphene and h-BN by a factor of 8 and 50, respectively.

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“…Surface wrinkling is a physical process that creates unique topographies in nature [5,6]. Nano/microscopic surface reliefs synthesized by wrinkling have been used for nano/microscopic wrinkled surfaces in optical [7] and electronic devices [8], surface-enhanced Raman spectroscopy substrates [9], the realization of tunable wettability [10], and adhesion [11], and cell culture scaffolds [12][13][14][15][16][17]. In the application for cell culture scaffolds, wrinkled surfaces with unique topographies have been used for cell proliferation [12], control of cellular alignment and differentiation [13,14,16], and spheroid generation [15,17].…”

Section: Introductionmentioning

confidence: 99%

Application of Bio-Based Wrinkled Surfaces as Cell Culture Scaffolds

Izawa

Okuda

Yonemura

et al. 2018

Colloids and Interfaces

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Microscopic surface architectures that can be easily manufactured have been in demand as mechano-structural cues for tissue engineering. Microscopic surface reliefs synthesized by wrinkling were expected as cell culture scaffolds for cell proliferation, control of cellular alignment and differentiation, and spheroid generation. We previously developed bio-based wrinkled films prepared via lignification-mimetic reactions and drying. Although these films are expected as a candidate for cell culture scaffolds, stability and morphology of the wrinkled surfaces in aqueous buffer solutions were not explored. Here, we investigate the surface morphologies of the wrinkled films in phosphate-buffered saline, and their application to 3T3 cell culture. The wrinkled film prepared with the immersion treatment at 40 • C maintained its wrinkled structure in phosphate-buffered saline even after five days, although the wrinkles were broadened by hydration of the skin layer. Interestingly, higher cell numbers were observed in the 3T3 cell culture using the wrinkled film than using flat film with the same surface composition. In addition, the high biocompatibility of the wrinkled film was confirmed by in vivo experiments. These results strongly encourage application of the wrinkled film as a mechano-structural cue. Studies of the advanced applications for the wrinkled films are now in progress.

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Self‐organized Polymer Wrinkles: A Lithography‐free Pathway for Surface‐enhanced Raman Scattering (SERS) Substrates

Cited by 16 publications

References 12 publications

Atmospheric oxidation and carbon contamination of silver and its effect on surface-enhanced Raman spectroscopy (SERS)

Atmospheric oxidation and carbon contamination of silver and its effect on surface-enhanced Raman spectroscopy (SERS)

Plasmon-Free Polymeric Nanowrinkled Substrates for Surface-Enhanced Raman Spectroscopy of Two-Dimensional Materials

Application of Bio-Based Wrinkled Surfaces as Cell Culture Scaffolds

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