RESUMEN
While gold nanoparticles (Au NPs) are widely used as surface-enhanced Raman spectroscopy (SERS) substrates, their agglomeration and dynamic movement under laser irradiation result in the major drawback in SERS applications, viz., the repeatability of SERS signals. We tune the optical and structural properties of size- and shape-modified Au NPs embedded in a thin silicon nitride (Si3N4) matrix by intense electronic excitation with swift heavy ion (SHI) irradiation with the aim of overcoming this classical SERS disadvantage. We demonstrate the shape evolution of a single layer of Au NPs inserted between amorphous Si3N4 thin films under fluences of 120 MeV Au9+ ions ranging between 1 × 1011 and 1 × 1013 ions cm-2. This shape modification results in the gradual blue shift of the localized surface plasmon resonance (LSPR) dip until 1 × 1012 ions/cm2 and then a sudden diminishment at 1 × 1013 ions/cm2. Finite domain time difference (FDTD) simulations further justify our experimental optical spectra. The dynamical NP aggregation and dissolution, in addition to NP elongation and deformation at different fluences, are noted from 2D grazing incidence small-angle X-ray scattering (GISAXS) profiles, as well as cross-sectional transmission electron microscopy (X-TEM). The systematic shape evolution of metal NPs embedded in the insulating matrix is shown to be due to thermal spike-induced localized melting and a localized pressure hike upon SHI irradiation. Utilizing this specific control over the characteristics of Au NPs, viz., shape, size, interparticle gap, and corresponding optical response via SHI irradiation, we demonstrate their applications as very stable SERS substrates, where the separation between NPs and analyte does not alter under laser illumination. Thus, these irradiated SERS active substrates with controlled NP size and gap provide the optimal conditions for creating localized electromagnetic hotspots that amplify the SERS signals, which do not alter with time or laser exposure. We found that the film irradiated with 1 × 1011 exhibits the highest SERS intensity due to its optimal NP size distribution and shape. Thus, not only our study provides a SERS substrate for stable and repeatable signals but also the understanding depicted here opens new research avenues in designing SERS substrates, photovoltaics, optoelectronic devices, etc. with ion beam irradiation.
RESUMEN
Two-dimensional-zero-dimensional plasmonic hybrids involving defective graphene and transition metals (DGR-TM) have drawn significant interest due to their near-field plasmonic effects in the wide range of the UV-vis-NIR spectrum. In the present work, we carried out extensive investigations on resonance Raman spectroscopy (RRS) and localized surface plasmon resonance (LSPR) from the various DGR-TM hybrids (Au, Ag, and Cu) using micro-Raman, spatial Raman mapping analysis, high-resolution transmission electron microscopy (HRTEM), and LSPR absorption measurements on defective CVD graphene layers. Further, electric field (E) mappings of samples were calculated using the finite domain time difference (FDTD) method to support the experimental findings. The spatial distribution of various in-plane and edge defects and defect-mediated interaction of plasmonic nanoparticles (NPs) with graphene were investigated on the basis of the RRS and LSPR and correlated with the quantitative analysis from HRTEM, excitation wavelength-dependent micro-Raman, and E-field enhancement features of defective graphene and defective graphene-Au hybrids before and after rapid thermal annealing (RTA). Excitation wavelength-dependent surface-enhanced Raman scattering (SERS) and LSPR-induced broadband absorption from DGR-Au plasmonic hybrids reveal the electron and phonon interaction on the graphene surface, which leads to the charge transfer from TM NPs to graphene. This is believed to be responsible for the reduction in the SERS signal, which was observed from the wavelength-dependent Raman spectroscopy/mappings. We implemented defective graphene and DGR-Au plasmonic hybrids as efficient SERS sensors to detect the Fluorescein and Rhodamine 6G molecules with a detection limit down to 10-9 M. Defective graphene and Au plasmonic hybrids showed an impressive Raman enhancement in the order of 108, which is significant for its practical application.
RESUMEN
Surface-enhanced Raman spectroscopy (SERS) is a highly sensitive and rapid detection technique that is used for detection of various analytes in trace quantities. We present a sensitive, large-area, and nanogap-rich SERS-active substrate by altering a thin gold (Au) film on the unpolished side of a single-side polished silicon wafer by repeated thermal deposition and annealing in an argon environment. The repeated thermal deposition and annealing process was compared on both sides of a one-side-polished silicon wafer; however, the rear side (etched/unpolished side) demonstrated a more enhanced Raman signal owing to the larger effective area. The proposed substrate can be fabricated easily, having a high density of hotspots distributed uniformly all over the substrate. This ensures easy, rapid, and sensitive detection of analytes with a high degree of reproducibility, repeatability, and acceptable uniformity. The optimized substrate shows a high degree of stability with time when exposed to the ambient environment for a longer duration of 148 days. The reported substrate can detect up to 10-11 M concentrations of 2,4,6-trinitrotoluene (TNT) and 2,4-dinitrotoluene (DNT), with limits of detection (LODs) of 1.22 and 1.26 ng/L, respectively. This work not only presents the efficient and sensitive SERS-active substrate but also shows the advantages of using the rear side of a one-side-polished silicon substrate as a SERS-active chip.
