We demonstrate the detection of molecular vibrations in single hemoglobin (Hb) protein molecules attached to isolated and immobilized silver nanoparticles by surface enhanced Raman scattering (SERS). A comparison between calculation and experiment indicates that electromagnetic field effects dominate the surface enhancement, and that single molecule Hb SERS is possible only for molecules situated between Ag particles. The vibrational spectra exhibit temporal fluctuations of unknown origin which appear to be characteristic of the single molecule detection limit.
The discovery of the enhancement of Raman scattering by molecules adsorbed on nanostructured metal surfaces is a landmark in the history of spectroscopic and analytical techniques. Significant experimental and theoretical effort has been directed toward understanding the surface-enhanced Raman scattering (SERS) effect and demonstrating its potential in various types of ultrasensitive sensing applications in a wide variety of fields. In the 45 years since its discovery, SERS has blossomed into a rich area of research and technology, but additional efforts are still needed before it can be routinely used analytically and in commercial products. In this Review, prominent authors from around the world joined together to summarize the state of the art in understanding and using SERS and to predict what can be expected in the near future in terms of research, applications, and technological development. This Review is dedicated to SERS pioneer and our coauthor, the late Prof. Richard Van Duyne, whom we lost during the preparation of this article.
We examine whether single molecule sensitivity in surface-enhanced Raman scattering (SERS) can be explained in the framework of classical electromagnetic theory. The influence of colloid particle shape and size, composition (Ag or Au) and interparticle separation distance on the wavelength-dependent SERS enhancement factor is reported. Our calculations indicate that the maximum enhancement factor achievable through electromagnetics is of the order 10(11). This is obtained only under special circumstances, namely at interstitial sites between particles and at locations outside sharp surface protrusions. The comparative rarity of such sites, together with the extreme spatial localization of the enhancement they provide, can qualitatively explain why only very few surface sites seem to contribute to the measured signal in single-molecule SERS experiments. Enhancement factors of the order 10(14)-10(15), which have been reported in recent experiments, are likely to involve additional enhancement mechanisms such as chemisorption induced resonance Raman effects.
The optical response of ring-shaped gold nanoparticles prepared by colloidal lithography is investigated. Compared to solid gold particles of similar size, nanorings exhibit a redshifted localized surface plasmon that can be tuned over an extended wavelength range by varying the ratio of the ring thickness to its radius. The measured wavelength variation is well reproduced by numerical calculations and interpreted as originating from coupling of dipolar modes at the inner and outer surfaces of the nanorings. The electric field associated with these plasmons exhibits uniform enhancement and polarization in the ring cavity, suggesting applications in near-infrared surface-enhanced spectroscopy and sensing.
In this paper, the electromagnetic interactions between noble metal nanoparticles are studied by measuring the extinction spectra of two-dimensional arrays of Au and Ag cylinders and trigonal prisms that have been fabricated with electron beam lithography. The nanoparticles are typically 200 nm in diameter and 35 nm in height; both hexagonal and square array patterns have been considered with lattice spacings that vary from 230 to 500 nm. The extinction spectra typically have a maximum in the 700-800 nm region of the spectrum, and this maximum blue shifts as lattice spacing is reduced, having typically a 40 nm decrease in λ max for a 100 nm decrease in lattice spacing. The results are similar for the different noble metals, array patterns, and nanoparticle shapes. The extinction spectra have been modeled using coupled dipole calculations, and the observed spectral variations are in good qualitative agreement with experimental data. Moreover, the computational analysis indicates that the blue shifts are due to radiative dipolar coupling between the nanoparticles and retardation effects. These effects result in a net depolarization of the dipole couplings for lattice spacings of 200-500 nm.
We report on the optical properties of single isolated silver nanodisks and pairs of disks fabricated by electron beam lithography. By systematically varying the disk size and surface separation and recording elastic scattering spectra in different polarization configurations, we found evidence for extremely strong interparticle interactions. The dipolar surface plasmon resonance for polarization parallel to the dimer axis exhibited a red shift as the interdimer separation was decreased; as expected from previous work, an extremely strong shift was observed. The scattering spectra of single particles and pairs separated by more than one particle radius can be well described by the coupled dipole approximation (CDA), where the particles are approximated as point dipoles using a modified dipole polarizability for oblate spheroids. For smaller particle separations (d < 20 nm), the simple dipole model severely underestimates the particle interaction, indicating the importance of multipolar fields and finite-size effects. The discrete dipole approximation (DDA), which is a finite-element method, describes the experimental results well even at d < 20 nm, including particles that have metallic bridges.
Realizing strong light-matter interactions between individual two-level systems and resonating cavities in atomic and solid state systems opens up possibilities to study optical nonlinearities on a single-photon level, which can be useful for future quantum information processing networks. However, these efforts have been hampered by unfavorable experimental conditions, such as cryogenic temperatures and ultrahigh vacuum, required to study such systems and phenomena. Although several attempts to realize strong lightmatter interactions at room temperature using plasmon resonances have been made, successful realizations on the single-nanoparticle level are still lacking. Here, we demonstrate the strong coupling between plasmons confined within a single silver nanoprism and excitons in molecular J aggregates at ambient conditions. Our findings show that deep subwavelength mode volumes V together with quality factors Q that are reasonably high for plasmonic nanostructures result in a strong-coupling figure of merit-Q= ffiffiffi ffi V p as high as ∼6 × 10 3 μm −3=2 , a value comparable to state-of-the-art photonic crystal and microring resonator cavities. This suggests that plasmonic nanocavities, and specifically silver nanoprisms, can be used for room temperature quantum optics. Strong light-matter interactions are not only interesting from a fundamental quantum optics point of view, e.g., for studying entanglement and decoherence, but also because of their relevance for high-end emerging applications such as quantum cryptography [1], quantum networks [2], single-atom lasers [3], ultrafast single-photon switches [4], and quantum information processing [5][6][7]. These phenomena rely on a quantum emitter strongly interacting with a resonant cavity, which leads to cavity and emitter mode hybridization and vacuum Rabi splitting [8]. In the time domain, these strong light-matter interactions manifest themselves as a coherent exchange of energy between the cavity and the emitter occurring on time scales faster than both cavity and emitter dissipative dynamics-a situation that is dramatically different from irreversible spontaneous emission. Traditionally, these quantum optical phenomena have been studied in atomic [9,10] and solid state systems [11][12][13], which are associated with considerable experimental challenges, such as ultrahigh vacuum, cryogenic temperatures, and fabrication issues.A possible solution to these challenges could be to use noble metal nanoparticles instead of photonic crystal and microring resonator cavities [14][15][16][17][18]. This is because metal nanostructures can trap electromagnetic fields on subwavelength scales as so-called surface plasmon excitations. These plasmonic nanocavities possess a number of desirable properties, such as room temperature operation, deep subwavelength mode volumes, and nanoscale dimensions that have been shown to lead to many remarkable phenomena including single-molecule Raman spectroscopy [19][20][21], tip-enhanced imaging [22], ultracompact nanolasers [23], ...
The optical responses of 75-150 nm diameter gold nanorings to changes in local refractive index have been quantified by near-infrared extinction spectroscopy and compared to DDA calculations and an analytical approach. The "bulk" refractive index sensitivities of gold nanorings are substantially (>5 times) larger than those of nanodisks with similar diameters. Nanorings retain a significantly larger sensitivity than nanodisks at the same spectral position, demonstrating a clear shape dependence that may correlate to a systematic difference in the influence of the dielectric substrate. The nanoring bulk refractive index sensitivity scales linearly with plasmon peak position. The spectral sensitivity to thin films of alkanethiols gave a shift of approximately 5.2 nm/CH2 unit while bulk sensitivities as high as 880 nm/RIU were observed, the highest such reported sensitivities. Both bulk and thin dielectric film sensitivities correlated well with theory. Real-time label-free monitoring of protein binding via molecular recognition was demonstrated.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
334 Leonard St
Brooklyn, NY 11211
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.