Surface-enhanced Raman spectroscopy (SERS) is currently experiencing a renaissance in its development driven by the remarkable discovery of single molecule SERS (SMSERS) and the explosion of interest in nanophotonics and plasmonics. Because excitation of the localized surface plasmon resonance (LSPR) of a nanostructured surface or nanoparticle lies at the heart of SERS, it is important to control all of the factors influencing the LSPR in order to maximize signal strength and ensure reproducibility. These factors include material, size, shape, interparticle spacing, and dielectric environment. All of these factors must be carefully controlled to ensure that the incident laser light maximally excites the LSPR in a reproducible manner. This article describes the use of nanosphere lithography for the fabrication of highly reproducible and robust SERS substrates for both fundamental studies and applications. Atomic layer deposition (ALD) is introduced as a novel fabrication method for dielectric spacers to study the SERS distance dependence and control the nanoscale dielectric environment. Wavelength scanned SER excitation spectroscopy (WS SERES) measurements show that enhancement factors approximately 10(8) are obtainable from NSL-fabricated surfaces and provide new insight into the electromagneticfield enhancement mechanism. Tip-enhanced Raman spectroscopy (TERS) is an extremely promising new development to improve the generality and information content of SERS. A 2D correlation analysis is applied to SMSERS data. Finally, the first in vivo SERS glucose sensing study is presented.
A new method to stabilize and functionalize surfaces for surface-enhanced Raman spectroscopy (SERS) is demonstrated. Atomic layer deposition (ALD) is used to deposit a sub-1-nm alumina layer on silver film-over-nanosphere (AgFON) substrates. The resulting overlayer maintains and stabilizes the SERS activity of the underlying silver while presenting the surface chemistry of the alumina overlayer, a commonly used polar adsorbent in chromatographic separations. The relative affinity of analytes for alumina-modified AgFON substrates can be determined by their polarity. On the basis of SERS measurements, dipicolinic acid displays the strongest binding to the ALD alumina-modified AgFON among a set of pyridine derivatives with varying polarity. This strong affinity for carboxylate groups makes the SERS substrate an ideal candidate for bacillus spores detection using the dipicolinate biomarker. The SERS signal from extracted dipicolinate was measured over the spore concentration range 10(-14)-10(-12) M to determine the saturation binding capacity of the alumina-modified AgFON surface. The adsorption constant was determined to be Kspore = 9.0 x 10(13) M(-1). A 10-s data collection time is capable of achieving a limit of detection of approximately 1.4 x 10(3) spores. The shelf life of prefabricated substrates is at least 9 months prior to use. In comparison to the bare AgFON substrates, the ALD-modified AgFON substrates demonstrate twice the sensitivity with 6 times shorter data acquisition time and 7 times longer temporal stability. ALD expands the palette of available chemical methods to functionalize SERS substrates, which will enable improved and diverse chemical control over the nature of analyte-surface binding for biomedical, homeland security, and environmental applications.
Atomic layer deposition (ALD) is used to deposit 1-600 monolayers of Al 2 O 3 on Ag nanotriangles fabricated by nanosphere lithography (NSL). Each monolayer of Al 2 O 3 has a thickness of 1.1 Å. It is demonstrated that the localized surface plasmon resonance (LSPR) nanosensor can detect Al 2 O 3 film growth with atomic spatial resolution normal to the nanoparticle surface. This is approximately 10 times greater spatial resolution than that in our previous long-range distance-dependence study using multilayer self-assembled monolayer shells. The use of ALD enables the study of both the long-and short-range distance dependence of the LSPR nanosensor in a single unified experiment. Ag nanoparticles with fixed in-plane widths and decreasing heights yield larger sensing distances. X-ray photoelectron spectroscopy, variable angle spectroscopic ellipsometry, and quartz crystal microbalance measurements are used to study the growth mechanism. It is proposed that the growth of Al 2 O 3 is initiated by the decomposition of trimethylaluminum on Ag. Semiquantitative theoretical calculations were compared with the experimental results and yield excellent agreement.
Surface-enhanced Raman spectroscopy (SERS) was used in this work to obtain highly detailed spectra of artists' red lake pigments and colorants. In the past, Raman spectroscopy has been successfully employed to identify many pigments and modern synthetic dyes. Unfortunately, red lake pigments and dyes commonly employed in artistic production from antiquity to the mid-nineteenth century are often extremely fluorescent, making identification with Raman spectroscopy difficult or impossible. This work presents an innovative SERS technique that quenches fluorescence, significantly enhances the weak Raman scattering effect, and requires very little sample material and minimal sample handling. A silver island film (AgIF), approximately 6-8 nm thick, is deposited on the substrate by electron beam (e-beam) deposition. The SERS-active surface is then analyzed with a confocal dispersive Raman microscope, at an excitation wavelength of 632.8 nm. Reference materials including the synthetic dyestuffs alizarin, purpurin, and eosin, high-purity carminic acid, and historic red lake pigments such as madder lake, cochineal, brazilwood, lac lake, and kermes were studied. The proposed method has great potential for the unambiguous identification of red dyes applied in different media on a variety of substrates, as demonstrated by the highly detailed Raman spectra presented here.
Nanosphere lithography (NSL) is an inexpensive, high throughput, materials general nanofabrication technique capable of producing a large variety of nanoscale structures including well-ordered 2 dimensional nanoparticle arrays. In this review, we will summarize the most recent advances in the fabrication of size-tunable nanoparticles using NSL. Four examples of new NSL-derived materials will be described: (1) The development of a method to release NSL nanoparticles from the substrate for applications in solution environments, (2) the fabrication of triangular nanoholes with reactive ion etching, (3) the electrochemical fine tuning of the structure of a silver nanoparticle and the wavelength of its localized surface plasmon resonance (LSPR), and (4) the growth of ultra thin protective dielectric layers on NSL-fabricated Ag nanotriangles using atomic layer deposition (ALD).
The work presented here describes the first steps toward designing a thermally robust surface-enhanced Raman spectroscopy (SERS) substrate with the potential to conduct in situ monitoring of catalytic reactions. Nanosphere lithography (NSL) fabricated SERS substrates were coated with thin (0.2-1.0 nm) films of atomic layer deposited (ALD) Al 2 O 3 . The thermal stability of these substrates was examined at various temperatures (100-500 °C) and over time (up to 6 h) in nitrogen. The results showed that ALD Al 2 O 3 coated nanoparticles maintained their original geometry significantly better than the bare Ag nanoparticles. While experiments showed that thicker ALD Al 2 O 3 coatings resulted in the most stable nanoparticle structure, ALD Al 2 O 3 coatings as thin as 0.2 nm resulted in thermally robust nanostructures as well. Additionally, the ALD Al 2 O 3 coated nanoparticles were heated under propane to mimic reaction conditions. These experiments showed that while the nanoparticle geometries were not as stable under reducing atmosphere conditions, they were much more stable than uncoated nanoparticles and therefore have the potential to be used for SERS monitoring of reactions conducted at elevated temperatures.
Nanosphere lithography (NSL) is combined with reactive ion etching (RIE) to fabricate ordered arrays of in-plane, triangular cross-section nanopores. Nanopores with in-plane widths ranging from 44 to 404 nm and depths ranging from 25 to 250 nm are demonstrated. The combination of angle-resolved nanosphere lithography (AR NSL) and RIE yields an additional three-fold reduction in nanopore size.
Silver film over nanospheres (AgFONs) were successfully employed as surface-enhanced Raman spectroscopy (SERS) substrates to characterize several artists' red dyes including: alizarin, purpurin, carminic acid, cochineal, and lac dye. Spectra were collected on sample volumes (1 x 10(-6) M or 15 ng/microL) similar to those that would be found in a museum setting and were found to be higher in resolution and consistency than those collected on silver island films (AgIFs). In fact, to the best of the authors' knowledge, this work presents the highest resolution spectrum of the artists' material cochineal to date. In order to determine an optimized SERS system for dye identification, experiments were conducted in which laser excitation wavelengths were matched with correlating AgFON localized surface plasmon resonance (LSPR) maxima. Enhancements of approximately two orders of magnitude were seen when resonance SERS conditions were met in comparison to non-resonance SERS conditions. Finally, because most samples collected in a museum contain multiple dyestuffs, AgFONs were employed to simultaneously identify individual dyes within several dye mixtures. These results indicate that AgFONs have great potential to be used to identify not only real artwork samples containing a single dye but also samples containing dyes mixtures.
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
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.