Characterization of 2D Transition Metal Dichalcogenides Through Anisotropic Exciton Behaviors.

This study reports the first attempt to characterize the quality, defects, and strain of as-grown monolayer transition metal dichalcogenide (TMDC)-based 2D materials through exciton anisotropy. A standard ellipsometric parameter (Ψ) to observe anisotropic exciton behavior in monolayer 2D materials is used. According to the strong exciton effect from phonon-electron coupling processes, the change in the exciton in the Van Hove singularity is sensitive to lattice distortions such as defects and strain. In comparison with Raman spectroscopy, the variations in exciton anisotropy in Ψ are more sensitive for detecting slight changes in the quality and strain of monolayer TMDC films. Moreover, the optical power requirement for TMDC characterization through exciton anisotropy in Ψ is ≈10-5 mW cm-2, which is significantly less than that of Raman spectroscopy (≈106 mW cm-2). The standard deviation of the signals varies with strain (defects) in Raman spectra and exciton anisotropies in Ψ are 0.700 (0.795) and 0.033 (0.073), indicating that exciton anisotropy is more sensitive to slight changes in the quality of monolayer TMDC films.

Wafer-scale nanocracks enable single-molecule detection and on-site analysis.

Large-area surface-enhanced Raman spectroscopy (SERS) sensing platforms displaying ultrahigh sensitivity and signal uniformity have potentially enormous sensing applicability, but they are still challenging to prepare in a scalable manner. In this study, silver nanopaste (AgNPA) was employed to prepare a wafer-scale, ultrasensitive SERS substrate. The self-generated, high-density Ag nanocracks (NCKs) with small gaps could be created on Si wafers via a spin-coating process, and provided extremely abundant hotspots for SERS analyses with ultrahigh sensitivity-down to the level of single molecules (enhancement factor: ca. 1010; detection limit: ca. 10-18 M)-and great signal reproducibility (variation: ca. 3.6%). Moreover, the Ag NCK arrays demonstrated broad applicability and practicability for on-site detection when combined with a portable 785 Raman spectrometer. This method allowed the highly sensitive detection of a diverse range of analytes (benzo[a]pyrene, di-2-ethylhexyl phthalate, aflatoxins B1, zearalenone, ractopamine, salbutamol, sildenafil, thiram, dimethoate, and methamidophos). In particular, pesticides are used extensively in agricultural production. Unfortunately, they can affect the environment and human health as a result of acute toxicity. Therefore, the simultaneous label-free detection of three different pesticides was demonstrated. Finally, the SERS substrates are fabricated through a simple, efficient, and scalable process that offers new opportunities for mass production.

Optical Inspection of 2D Materials: From Mechanical Exfoliation to Wafer-Scale Growth and Beyond.

Optical inspection is a rapid and non-destructive method for characterizing the properties of two-dimensional (2D) materials. With the aid of optical inspection, in situ and scalable monitoring of the properties of 2D materials can be implemented industrially to advance the development and progress of 2D material-based devices toward mass production. This review discusses the optical inspection techniques that are available to characterize various 2D materials, including graphene, transition metal dichalcogenides (TMDCs), hexagonal boron nitride (h-BN), group-III monochalcogenides, black phosphorus (BP), and group-IV monochalcogenides. First, the authors provide an introduction to these 2D materials and the processes commonly used for their fabrication. Then they review several of the important structural properties of 2D materials, and discuss how to characterize them using appropriate optical inspection tools. The authors also describe the challenges and opportunities faced when applying optical inspection to recently developed 2D materials, from mechanically exfoliated to wafer-scale-grown 2D materials. Most importantly, the authors summarize the techniques available for largely and precisely enhancing the optical signals from 2D materials. This comprehensive review of the current status and perspective of future trends for optical inspection of the structural properties of 2D materials will facilitate the development of next-generation 2D material-based devices.

Diverse Substrate-Mediated Local Electric Field Enhancement of Metal Nanoparticles for Nanogap-Enhanced Raman Scattering.

The localized surface plasmon resonance of plasmonic nanoparticles (NPs) can be coupled with a noble metal substrate (S) to induce a localized augmented electric field (E-field) concentrated at the NP-S gap. Herein, we analyzed the fundamental near-field properties of metal NPs on diverse substrates numerically (using the 3D finite-difference time-domain method) and experimentally [using surface-enhanced Raman scattering (SERS)]. We systematically examined the effects of plasmonic NPs on noble metals (Ag and Au), non-noble metals (Al, Ti, Cu, Fe, and Ni), semiconductors (Si and Ge), and dielectrics (TiO2, ZnO, and SiO2) as substrates. For the AgNPs, the Al (11,664 times) and Si (3969 times) substrates produced considerable E-field enhancements, with Al in particular generating a tremendous E-field enhancement comparable in intensity to that induced by a Ag (28,224 times) substrate. Notably, we found that a superior metallic character of the substrate gave rise to easier induction of image charges within the metal substrate, resulting in a greater E-field at the NP-S gap; on the other hand, the larger the permittivity of the nonmetal substrate, the greater the ability of the substrate to store an image charge distribution, resulting in stronger coupling to the charges of localized surface plasmon resonance oscillation on the metal NP. Furthermore, we measured the SERS spectra of rhodamine 6G (a commonly used Raman spectral probe), histamine (a biogenic amine used as a food freshness indicator), creatinine (a kidney health indicator), and tert-butylbenzene [an extreme ultraviolet (EUV) lithography contaminant] on AgNP-immobilized Al and Si substrates to demonstrate the wide range of potential applications. Finally, the NP-S gap hotspots appear to be widely applicable as an ultrasensitive SERS platform (∼single-molecule level), especially when used as a powerful analytical tool for the detection of residual contaminants on versatile substrates.

Manipulating the distribution of electric field intensity to effectively enhance the spatial and spectral fluorescence intensity of fluorescent nanodiamonds.

Fluorescent nanodiamonds (FNDs) having nitrogen-vacancy (NV) centers have drawn much attention for their biocompatibility and stable optical properties. Nevertheless, the NV centers are located in the interior of the FNDs, and it has not been possible to increase the fluorescence intensity of FNDs efficiently using previously developed enhancement methods. In this paper, we present a simple nanocavity structure that enhances the fluorescence intensity of FNDs. The designed Al/SiO2 nanocavities are stable and inexpensive, and provide a large region for efficient enhancement of fluorescence that can cover most 100 nm FNDs. By tuning the thickness of the capping SiO2 layer of the Al/SiO2 nanocavities, the distributions of both the spatial and spectral electric field intensities of the FNDs could be controlled and manipulated. In general, the FNDs were excited using a green-yellow laser; the broadband fluorescence of the FNDs comprised the emissions from neutral (NV0) and negatively charged (NV-) NV centers. To enhance the fluorescence intensity from the NV- centers of the FNDs, we designed an Al/70 nm SiO2 nanocavity to function at excitation and emission wavelengths of 633 and 710 nm, respectively, allowing the NV- centers to be excited efficiently; as a result, we achieved an enhancement in fluorescence intensity of 11.2-fold. Moreover, even when we covered 100 nm FNDs with polyglycerol (forming p-FND), the fluorescence intensities of the p-FND particles placed on the nanocavities remained greatly enhanced.

Enhancing Raman signals through electromagnetic hot zones induced by magnetic dipole resonance of metal-free nanoparticles.

In this study, we found that the large area of electromagnetic field hot zone induced through magnetic dipole resonance of metal-free structures can greatly enhance Raman scattering signals. The magnetic resonant nanocavities, based on high-refractive-index silicon nanoparticles (SiNPs), were designed to resonate at the wavelength of the excitation laser of the Raman system. The well-dispersed SiNPs that were not closely packed displayed significant magnetic dipole resonance and gave a Raman enhancement per unit volume of 59 347. The hot zones of intense electric field were generated not only within the nonmetallic NPs but also around them, even within the underlying substrate. We observed experimentally that gallium nitride (GaN) and silicon carbide (SiC) surfaces presenting very few SiNPs (coverage: <0.3%) could display significantly enhanced (>50%) Raman signals. In contrast, the Raman signals of the underlying substrates were not enhanced by gold nanoparticles (AuNPs), even though these NPs displayed a localized surface plasmon resonance (LSPR) phenomenon. A comparison of the areas of the electric field hot zones (E 2 > 10) generated by SiNPs undergoing magnetic dipole resonance with the electric field hot spots (E 2 > 10) generated by AuNPs undergoing LSPR revealed that the former was approximately 70 times that of the latter. More noteworthily, the electromagnetic field hot zone generated from the SiNP is able to extend into the surrounding and underlying media. Relative to metallic NPs undergoing LSPR, these nonmetallic NPs displaying magnetic dipole resonance were more effective at enhancing the Raman scattering signals from analytes that were underlying, or even far away from, them. This application of magnetic dipole resonance in metal-free structures appears to have great potential for use in developing next-generation techniques for Raman enhancement.