Hot‐Spot Engineering Through Soft Actuators for Surface‐Enhanced Raman Spectroscopy (SERS) Applications

Liman, Gorkem; Yildiz, Emrecan; Ilhan, Hasan; Çetin, Arif E.; Demirel, Gökhan

doi:10.1002/adom.202100009

Cited by 6 publications

(9 citation statements)

References 34 publications

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“…Hot-spot formations, where the electromagnetic field is maximized, play a key role in SERS applications. ,− To this end, we designed thermoresponsive polymer brushes to generate hot-spots in a controlled manner. In our design, plasmonic particles-modified polymer brushes generate hot-spots through the phase transition of the polymer at a temperature higher than the lower critical solution temperature (LCST) of the polymer (∼25 °C, please see Supporting Information, Figure S4) and leading to a magnification in the electromagnetic field that yields a stronger Raman signal intensity compared to the unshrunk form of polymer brushes.…”

Section: Resultsmentioning

confidence: 99%

“…To generate hot-spots in SERS substrates, a distance less than 10 nm should exist between plasmonic materials. To this end, several top-down and bottom-up methods have recently been demonstrated for the precise tuning of hot-spot generation. − However, alternative approaches are still necessary, not only to realize real-life SERS applications but also to further explicate the EM mechanism of SERS.…”

Section: Introductionmentioning

confidence: 99%

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Thermoresponsive Polymer Brush-Decorated 3-D Plasmonic Gold Nanorod Arrays as an Effective Plasmonic Sensing Platform

Hukum

Çaykara

Demirel

2023

ACS Appl. Polym. Mater.

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Molecular sensing based on plasmonic materials is of great interest not only for basic scientific research but also for real-life applications. For plasmonic sensing, tunable hot-spot generation, in which the electromagnetic field is maximized, plays a key role. Herein, we developed a platform consisting of a thermoresponsive polymer brush with colloidal plasmonic particles and 3-D ordered/vertically aligned gold nanorod (AuNR) arrays for surface-enhanced Raman spectroscopy (SERS) applications. Poly(di(ethylene glycol) methyl ether methacrylate) brushes were synthesized via the interface-mediated reversible addition fragmentation chain transfer polymerization method. 3-D AuNR arrays were also fabricated by the oblique angle physical vapor deposition method. Highdensity hot-spot generation on the platforms was achieved by reducing the distance between the plasmonic particles and the underlying AuNR array as a result of phase transition of the polymer brushes. The design and optimization of such a platform will pave the way for molecular detection applications in a broad range of fields such as medicine, environmental protection, food safety, and homeland security.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Thermoresponsive Polymer Brush-Decorated 3-D Plasmonic Gold Nanorod Arrays as an Effective Plasmonic Sensing Platform

Hukum

Çaykara

Demirel

2023

ACS Appl. Polym. Mater.

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“…In addition, LSPR wavelength shift after the bending process could only have a minor role in the enhancement mechanism, as we previously demonstrated. [ 48 ]…”

Section: Resultsmentioning

confidence: 99%

“…[51,52] Also, on the basis of our previous experiments, 24 h immersion time into an aqueous AuNPs solution was employed. [48] Figure 2a shows the SEM image of a AuNP decorated cylinder. The AuNP density on the cylinder surface was calculated to be 4.48 Â 10 10 nanoparticle cm À2 , which indicates a highly favorable morphology for hot-spot formation during physical contact.…”

Section: Resultsmentioning

confidence: 99%

“…Considering the great potential and advantages of soft actuators, we recently demonstrated that the irreversible folding of a prestrained polystyrene (PS) sheet decorated with plasmonic structures enables hot‐spot formation by controlling the temperature distribution on the material. [ 48 ] The fabricated platforms were able to demonstrate a Raman signal enhancement as large as ≈70‐fold due to folding of their arms. However, irreversible folding behavior of PS sheet, possibility of thermal degradation of analyte molecules during folding process, and limited generation and distribution of hot‐spots on platforms are the main drawbacks of this platform.…”

Section: Introductionmentioning

confidence: 99%

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Dynamic Tuning of Plasmonic Hot‐Spot Generation through Cilia‐Inspired Magnetic Actuators

Liman

Ergene

Yildiz

et al. 2023

Advanced Intelligent Systems

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Soft actuators that draw inspiration from nature are powerful and versatile tools for both technological applications and fundamental research, yet their use in hot‐spot engineering is very limited. Conventional hot‐spot engineering methods still suffer from complexity, high process cost, and static generation of hot‐spots, thus, underperforming particularly in the application side. Herein, we demonstrate a strategy based on plasmonic nanoparticles decorated cilia‐inspired magnetic actuators that enable highly accessible millimeter‐sized hot‐spot generation via bending motion under a magnetic field. The hot‐spot formation is shown to be reversible and tunable, and leads to excellent Raman signal enhancements of up to ≈120 folds compared to the unactuated platforms. Accessible electromagnetic field magnification in the platforms can be manipulated by controlling magnetic field strength, which is further supported by finite difference time domain (FDTD) simulations. As a proof‐of‐concept demonstration, a centipede‐inspired robot is fabricated and used for sample collection/analysis in a target environment. Our results demonstrate an effective strategy in soft actuator platforms for reversible and tunable large‐area hot‐spot formation, which provides a promising guidance toward studying the fundamentals of hot‐spot generation and advancing real‐life plasmonic applications.

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Wafer‐Scale 2H‐MoS₂ Monolayer for High Surface‐enhanced Raman Scattering Performance: Charge‐Transfer Coupled with Molecule Resonance

Chen

et al. 2022

Adv Materials Technologies

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in 1997, this technique has been becoming one of the key technologies in chemical analysis, chemosensors, biomedical applications, etc. [1] To reveal the mechanism and improve the enhancement factor (EF), a large number of experimental and theoretical works were carried out. [2] For the substrates with noble metal nanoparticles, the electromagnetic mechanism arising from localized surface plasmons is dominantly responsible for the ultrahigh EF. [3] While the chemical mechanism, which is originated from the charge transfer between the substrate and absorbed molecules, is attributed to the SERS mechanism in the semiconducting substrates. [1c,4] Additionally, the accompanied resonances in the charge transfer, such as molecule resonance and surface plasmon, have also attributed to the enhanced SERS in the molecule-semiconductor system. [2d,5] As semiconductors are abundant, cheap, and stable, and may be easily integrated into modern electronic devices, they have been widely investigated. However, their performance is still poorer than those of noble metals. Therefore, various strategies, such as doping, defect engineering, morphology optimization, hybridization, and phase-transition control, [6] have been explored to improve the charge transfer asThe surface-enhanced Raman scattering (SERS) as a novel and efficient analytic technique to probe molecules has attracted tremendous attention. Semiconducting substrates have been widely investigated for their applications into SERS because of their easy integration with electronic devices. In this work, a wafer-scale semiconducting MoS 2 monolayer (2H-MoS 2 -ML) without additional treatment is used as the SERS substrate, which shows the naturally formed MoS 2 ML has excellent chemical stability, high uniformity, and high sensitivity. It is found that the detection concentration limit can reach 1 × 10 −8 m and the enhancement factor is about 4.5 × 10 6 for the rhodamine 6G (R6G) under a 532 nm excitation laser, which is the highest SERS performance observed on 2H-MoS 2 -ML up to now. The experimental and computational studies reveal that the photo-enhanced charge transfer coupled with molecule resonance contribute to remarkable SERS. In addition to R6G, 2H-MoS 2 -ML shows good SERS signals on the detection of amaranth and crystal violet too. The findings not only provide an insightful understanding of the mechanism for the improved SERS performance of semiconducting transition-metal dichalcogenides (TMDs) MLs, but are helpful for the design of novel SERS substrates. It is expected that the wafer-scale TMDs may find practical applications in SERS.

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Hot‐Spot Engineering Through Soft Actuators for Surface‐Enhanced Raman Spectroscopy (SERS) Applications

Cited by 6 publications

References 34 publications

Thermoresponsive Polymer Brush-Decorated 3-D Plasmonic Gold Nanorod Arrays as an Effective Plasmonic Sensing Platform

Thermoresponsive Polymer Brush-Decorated 3-D Plasmonic Gold Nanorod Arrays as an Effective Plasmonic Sensing Platform

Dynamic Tuning of Plasmonic Hot‐Spot Generation through Cilia‐Inspired Magnetic Actuators

Wafer‐Scale 2H‐MoS₂ Monolayer for High Surface‐enhanced Raman Scattering Performance: Charge‐Transfer Coupled with Molecule Resonance

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Hot‐Spot Engineering Through Soft Actuators for Surface‐Enhanced Raman Spectroscopy (SERS) Applications

Cited by 6 publications

References 34 publications

Thermoresponsive Polymer Brush-Decorated 3-D Plasmonic Gold Nanorod Arrays as an Effective Plasmonic Sensing Platform

Thermoresponsive Polymer Brush-Decorated 3-D Plasmonic Gold Nanorod Arrays as an Effective Plasmonic Sensing Platform

Dynamic Tuning of Plasmonic Hot‐Spot Generation through Cilia‐Inspired Magnetic Actuators

Wafer‐Scale 2H‐MoS2 Monolayer for High Surface‐enhanced Raman Scattering Performance: Charge‐Transfer Coupled with Molecule Resonance

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Product

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Wafer‐Scale 2H‐MoS₂ Monolayer for High Surface‐enhanced Raman Scattering Performance: Charge‐Transfer Coupled with Molecule Resonance