Highly efficient SERS substrates with different Ag interparticle nanogaps based on hyperbolic metamaterials

Shafi, Muhammad; Liu, Runcheng; Zha, Zhipeng; Li, Can; Du, Xin; Wali, Sartaj; Jiang, Shouzhen; Man, Baoyuan; Liu, Mei

doi:10.1016/j.apsusc.2021.149729

Cited by 34 publications

(24 citation statements)

References 28 publications

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“…Various nanoparticle based SERS substrates in conjunction with HMTMs have been considered to the further enhance the field enhancement provided by the nanoparticles [11][12][13] . However, these approached rely on the surface plasmon polariton modes of the nanoparticles which is limited by resonance, and are highly dependent on the nanoparticle distribution on the substrate, which can be challenging to control.…”

Section: Introductionmentioning

confidence: 99%

Hyperbolic metamaterials for large-area Surface-Enhanced Raman Scattering (SERS) sensing

Gulseren

Domulevicz

Gómez‐Díaz

2022

Enhanced Spectroscopies and Nanoimaging 2022

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Typical surface-enhanced Raman scattering (SERS) approaches rely on localized surface plasmon resonances that provide a significant enhancement of the localized electric field. Unfortunately, this technique faces challenges in terms of repeatability, which appears due to the strong dependence of the field enhancement on the surface roughness and the presence of hot-spots in nanostructures; and adequate excitation, as the laser beam must be tuned at a very specific wavelength that corresponds to the resonant frequency of the system. Hyperbolic metamaterials (HMTMs), a type of composite materials whose effective permittivity changes as a function of the electric field polarization, can effectively address these challenges because they support bulk and surface hyperbolic modes able to drastically boost the local fields over a broadband portion of the electromagnetic spectrum. In fact, the frequency response of these artificial materials can be manipulated by adjusting the system composing materials and filling ratios. This work aims to explore the potential of HMTMs to enhance the SERS of molecules located nearby and to address some of the challenges faced by common SERS platforms. To this purpose, we focus on Au/SiO2 HMTMs stacks that exhibit a hyperbolic dispersion for wavelengths larger than ~580 nm. A prototype has been fabricated and characterized using TEM and ellipsometry measurements. Power-dependent SERS measurements were obtained for a monolayer of biphenyl-4,4’-dithiol (BPDT) molecules self-assembled onto the HMTM surface and a gold-based control sample. HMTMs provide repeatable SERS detection with low laser powers <900µW and integration times <97ms (~30X and ~100X lower than control, respectively) over a large surface area, exhibiting a performance like complex TERS systems.

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Section: Introductionmentioning

confidence: 99%

Hyperbolic metamaterials for large-area Surface-Enhanced Raman Scattering (SERS) sensing

Gulseren

Domulevicz

Gómez‐Díaz

2022

Enhanced Spectroscopies and Nanoimaging 2022

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“…The dispersion relation represents the allowed propagation directions and their corresponding wavelengths. Moreover, the photonic density of states (PDOS) increases because the unique hyperbolic unlimited wave vectors (i.e., high- k modes) of the iso-frequency contour in the momentum space. − Once the metal and the dielectric interface is thin and flat, a collective oscillation of electrons called surface plasmon polaritons (SPPs) is confined to the interface. In addition, the high- k modes that emerge from the intercoupling effect of SPPs are realized as the volume plasmon polaritons, resulting in an enhancement of charge-transfer dynamics, an improvement in fluorescence emission, incremented transition rates of optical gain media, and a higher possibility of achieving laser action. , …”

Section: Introductionmentioning

confidence: 99%

Generation of Silver Metal Nanocluster Random Lasing

et al. 2021

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Atomically precise molecular-like metal nanoclusters (MNCs) exhibit unique properties, such as strong photoluminescence and absorption with inherent biocompatibility, which enable us to extend their applications to chemical sensing, biomedical imaging, optoelectronics, and many other areas. However, stimulated laser emission is greatly desirable to upgrade their more advanced functionalities. Here we provide a plausible approach to achieve this outstanding characteristic from MNCs. Quite interestingly, by integrating hyperbolic metamaterials (HMMs) with highly luminescent silver metal nanoclusters (Ag-TSA MNCs), a strong stimulated emission (random lasing action) with a low threshold of ∼0.5 kW cm −2 is discovered. The light emission is enhanced by ∼35 times when the solid-state assembly of Ag-TSA MNCs is integrated with HMM in comparison with that with a silicon substrate. The highk modes excited by the HMM offer the possibility of forming the coherent closed feedback loops necessary for random lasing actions, thereby decreasing the energy loss associated with the photons' propagation in the matrix. The simulations derived from the finite-difference time-domain method support the experimental results. Our study shown here makes an initial step to demonstrate stimulated laser action from metal nanoclusters. It is believed that there exist many other alternatives for exploring this emerging research topic for the future development of cost-effective and biocompatible optoelectronic devices.

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“…Using small regions such as sharp corners, tips, and interparticle gaps − with a much higher electromagnetic field providing a hot spot effect, constructive plasmonic coupling between neighboring metallic nanoparticles enables explosive SERS signal enhancement. Consequently, the optical excitation of the intensified electric fields due to localized surface plasmon resonance provided distinct Raman scattering signals when targeting molecules indirectly in contact or very closely approaching nanoscale metallic substrates. − Thanks to the recent great improvement in nanotechnology along with nanofabrication, it is possible to control the distance between metal nanoparticles for the improved coupling resonances of the surface electromagnetic fields and the hot spot effect for SERS signals. , …”

Section: Introductionmentioning

confidence: 99%

Thermoresponsive SERS Nanocapsules Constructed by Linear-Dendritic Poly(urea/malonamide) for Tunable Biomolecule Detection

Cheng

Chuang

Wang

et al. 2021

ACS Appl. Polym. Mater.

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In this work, thermoresponsive core–shell micelle-embedded silver nanoparticles (AgNPs) were prepared from a series of monodisperse linear-dendritic poly(urea/malonamide). Through efficient iterative synthesis, well-defined dendritic amphiphiles bearing dual functionality provide nucleation sites as excellent templates for immobilizing AgNPs on one end, while oligoethers anchor water to stabilize these micelles in water as polymer dispersions. During the heating process, linear-dendritic poly(urea/malonamide) with various ratios of hydrophilic/hydrophobic segments resulted in the size-dependent lowest critical solution temperature (LCST), ranging from 72 to 54 °C in aqueous media. As a result, the gap distances between AgNPs could be manipulated, resulting in a stronger hot spot effect using thermoresponsive nanocapsules for surface-enhanced Raman scattering (SERS) analysis. Consequently, the signal was enhanced at temperatures over the LCST. For AgNPs@TD-G1.5 thermoresponsive SERS nanocapsules, an ∼33 times enhancement during the LCST transition was obtained. The high sensitivity and stability of the intelligent AgNPs@thermoresponsive SERS nanocapsules endow them with great potential in the rapid SERS detection of small-molecule analytes by adsorbing analytes at room temperature (below the LCST) and encapsulating the analytes into micelles at high temperatures (above the LCST) in the application of monitoring trace-level and diverse analytes.

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Highly efficient SERS substrates with different Ag interparticle nanogaps based on hyperbolic metamaterials

Cited by 34 publications

References 28 publications

Hyperbolic metamaterials for large-area Surface-Enhanced Raman Scattering (SERS) sensing

Hyperbolic metamaterials for large-area Surface-Enhanced Raman Scattering (SERS) sensing

Generation of Silver Metal Nanocluster Random Lasing

Thermoresponsive SERS Nanocapsules Constructed by Linear-Dendritic Poly(urea/malonamide) for Tunable Biomolecule Detection

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