Yun Han

Effect of Oxidation on Surface-Enhanced Raman Scattering Activity of Silver Nanoparticles: A Quantitative Correlation

We quantitatively studied, using X-ray photoelectron spectroscopy (XPS), oxidation of substrate-immobilized silver nanoparticles (Ag NPs) in a wide range of conditions, including exposure to ambient air and controlled ozone environment under UV irradiation, and we correlated the degree of silver oxidation with surface-enhanced Raman scattering (SERS) enhancement factors (EFs). The SERS activity of pristine and oxidized Ag NPs was assessed by use of trans-1,2-bis(4-pyridyl)ethylene (BPE) and sodium thiocynate as model analytes at the excitation wavelength of 532 nm. Our study showed that the exposure of Ag NPs to parts per million (ppm) level concentrations of ozone led to the formation of Ag(2)O and orders of magnitude reduction in SERS EFs. Such an adverse effect was also notable upon exposure of Ag NPs under ambient conditions where ozone existed at parts per billion (ppb) level. The correlated XPS and SERS studies suggested that formation of just a submonolayer of Ag(2)O was sufficient to decrease markedly the SERS EF of Ag NPs. In addition, studies of changes in plasmon absorption bands pointed to the chemical enhancement as a major reason for deterioration of SERS signals when substrates were pre-exposed to ambient air, and to a combination of changes in chemical and electromagnetic enhancements in the case of substrate pre-exposure to elevated ozone concentrations. Finally, we also found UV irradiation and ozone had a synergistic effect on silver oxidation and thus a detrimental effect on SERS enhancement of Ag NPs and that such oxidation effects were analyte-dependent, as a result of inherent differences in chemical enhancements and molecular binding affinities for various analytes.

SERS Not To Be Taken for Granted in the Presence of Oxygen

Oxidation of the Ag nanoparticle surface has a dramatic effect on the adsorption, orientation, and SERS detection limit of nitroaromatic molecules in aqueous solutions. Ultrasensitive SERS detection of p-nitrophenol can be achieved when oxidation of surface-immobilized Ag nanoparticles is inhibited by replacing the oxygen dissolved in water with argon gas. The presence of silver oxide at the nanoparticle surface hinders charge transfer between the aromatic ring and the underlying Ag metal surface and drastically decreases the overall detection sensitivity.

Towards Full-Length Accumulative Surface-Enhanced Raman Scattering-Active Photonic Crystal Fibers

The integration of microfluidics with photonics on a single platform using well-established planar device technology has led to the emergence of the exciting field of optofluidics. As both a light guide and a liquid/gas transmission cell, photonic crystal fiber (PCF, also termed microstructured or holey fiber), synergistically combines microfluidics and optics in a single fiber with unprecedented light path length not readily achievable using planar optofluidics. PCF, an inherent optofluics platform, offers excellent prospects for a multitude of scientific and technological applications. The accessibility to the air channels of PCF has also opened up the possibility for functionalization of the channel surfaces (silica in nature) at the molecular and the nanometer scales, in particular to impart the functionality of surface-enhanced Raman scattering (SERS) in PCF for sensing and detection. SERS, an ever advancing research field since its discovery in the 1970s, has tremendous potential for label-freemolecular identification at trace or even single-molecule levels due to up to 10 increase in the Raman scattering cross-section of a molecule in the presence of Ag or Au nanostructures. Seminal work has been reported on the development of 1D and 2D SERS substrates for a variety of sensing applications. The use of 3D geometry, i.e., substrates obtained by the deposition of noble nanoparticles onto porous silicon or porous aluminum membrane offered additional advantages of increased SERS intensity due to increased SERS probing area, as well as the membrane waveguiding properties. Specifically, several orders of magnitude higher SERS intensity, affording picoor zeptogram-level detection of explosives, has been demonstrated with porous alumina membranes containing 60-mm-long nanochannels, as compared to a solid planar substrate. SERS-active PCF optofluidics, as a special fiber optic SERS platform, offers easy system integration for in situ flow-through detection, and, more importantly, much longer light interaction length with analyte, thus promising to open a new vista in chemical/biological sensing, medical diagnosis, and process monitoring, especially in geometrically confined or sampling volume-limited systems. Various attempts have been made over the last several years to integrate SERS with the PCF platform by incorporating Ag or Au nanostructures albeit inside a very limited segment (typically a few centimeters) of the fiber air channels. Examples include deposition of Ag particulates and thin films by chemical vapor deposition at high pressure or coating of Ag and Au nanoparticles using colloidal solutions driven into the microscopic air channels via capillary force with backscattering as the typical data acquisition mode. Building uniform SERS functionality throughout the length of the PCF while preserving its light guide characteristics has remained elusive as measured Raman intensity is a combination of the accumulative gain from Raman scattering and the continuous loss from nanoparticle-induced light attenuation over the path length. As a result, we have recommended and recently described in a brief study forward scattering as a more suitable detection mode to unambiguously assess the SERS-active nature of PCF. To the best of our knowledge, this article is the first report of net accumulative SERS from the full-length Ag-nanoparticlefunctionalized PCFs. The finding has been enabled by a fine control of the coverage density of Ag nanoparticles and studies of a competitive interplay between SERS gain and light attenuation in the Raman intensity with PCFs of varying length. Using two different types of PCF, i.e., solid-core PCF and hollow-core PCF, we show that Raman gain in PCF prevails at relatively low nanoparticle coverage density (below 0.5 particlemm ), allowing full benefit of accumulation of Raman intensity along the fiber length for robust SERS sensing and enhanced measurement sensitivity. Light attenuation dominates at higher nanoparticle coverage density, however, diminishing the path-length benefit. Shown in Figure 1 are cross-sectional scanning electron microscopy (SEM) images of solid-core PCFand hollow-core PCF used in this work. Also depicted in the figure is the light-guide process in the corresponding PCFs that contain immobilized Ag nanoparticles and are filled with aqueous solution throughout the cladding air channels for solid-core PCFand in the center air core only for hollow-core PCF. Note that light is guided via total internal reflectance in both cases. The presence of the aqueous solution in the cladding air channels does not fundamentally change the contrast of the higher index silica core and the lower index liquid-silica cladding in the solid-core PCF. The selective

Structure fits the purpose: photonic crystal fibers for evanescent-field surface-enhanced Raman spectroscopy

We report numerical simulation and hyperspectral Raman imaging of three index-guiding solid-core photonic crystal fibers (PCFs) of different air-cladding microstructures to assess their respective potential for evanescent-field Raman spectroscopy, with an emphasis on achieving surface-enhanced Raman scattering (SERS) over the entire fiber length. Suspended-core PCF consisting of a silica core surrounded by three large air channels conjoined by a thin silica web is the most robust of the three SERS-active PCFs, with a demonstrated detection sensitivity of 1x10(-10) M R6G in an aqueous solution of only approximately 7.3 microL sampling volume.

Forward-propagating surface-enhanced Raman scattering and intensity distribution in photonic crystal fiber with immobilized Ag nanoparticles

A 30 cm long solid-core photonic crystal fiber (PCF) with immobilized and discrete Ag nanoparticles was used to obtain forward-propagating surface-enhanced Raman scattering (SERS) of 2 microM Rhodamine 6G (R6G) aqueous solution filled in the cladding air channels. The intensity distributions of characteristic Raman vibrational bands of silica and R6G in PCF were mapped for the first time to our knowledge by hyperspectral Raman imaging. We show that the measured SERS intensity arises exclusively from the forward-propagating core mode as a result of evanescent-field interaction with R6G in the innermost ring of the cladding air channels.

Index-guiding liquid-core photonic crystal fiber for solution measurement using normal and surface-enhanced Raman scattering

We have explored the use of index-guiding liquid-core (LC) photonic crystal fiber (PCF) as a robust platform for measurements of solutions of trace volume using normal and surface-enhanced Raman scattering (SERS). The LC PCF was fabricated by selectively sealing the cladding air channels at the distal ends of a hollow-core PCF while leaving the center core open, using a fusion splicer. Utilizing a 30-cm-long LC PCF with the entire center core filled with the ~0.1-µL solution of interest, we have obtained normal Raman spectra of water, ethanol, and 1 vol% ethanol in water. Sensitive and reproducible SERS detection of 1.7×10−7 M thiocyanate anions (14 ppb of NaSCN) in water has also been achieved.

Photonic crystal fiber as an optofluidic platform for surface-enhanced Raman scattering

As both a waveguide and a gas/liquid transmission cell, photonic crystal fiber (PCF) allows synergistic integration of optics and microfluidics to form an unconventional optofluidic platform with long interaction path. In this paper, we report our strategy to achieve surface-enhanced Raman scattering (SERS) PCF optofluidics by polyelectrolyte-mediated immobilization of Ag nanoparticles (NPs) inside the fiber air channels. Through forward propagating Raman measurements and hyperspectral Raman imaging, we demonstrate the realization of SERS-active PCF optofluidics with accumulative Raman signal gain along the entire fiber length using both solid-core PCF (SC PCF) and hollow-core PCF (HC PCF). By numerical simulation and Raman measurements, we show that suspended-core PCF (SP PCF) consisting of a silica core surrounded by three large air channels conjoined by a thin silica web is the most robust platform of the three SC PCF microstructures investigated for evanescent-field SERS spectroscopy.

PCF with Immobilized Silver Nanoparticles as an Optofluidic SERS Sensing Platform

The unique feature of photonic crystal fiber (PCF) both as a light guide and a liquid transmission cell allows synergistic integration of optics and microfluidics to form an unconventional optofluidic platform of long interaction path limited only by the fiber length. We report the strategy and methods in realizing full-length surface-enhanced Raman scattering (SERS) PCF optofluidics by immobilization of negatively charged Ag nanoparticles (NP) through polyelectrolyte-mediated approach or direct deposition of positively charged Ag NP on the PCF air channels. Through forward propagating Raman measurements, we demonstrate the full-length SERS-active PCF optofluidics with accumulative Raman signal gain along the entire fiber length. We show SERS measurements of 1x10-7 M (~48 ppb) Rhodamine 6G and 1x10-8 M (~0.8 ppb) sodium thiocyanate in a minute volume of ~10-7-10-8 liter aqueous solution using PCF with immobilized Ag NP over ~20 cm in length. The combination of high detection sensitivity and small sampling volume renders the SERS-active PCF optofluidic platform excellent potential for a multitude of applications ranging from label-free chemical and biological sensing to process monitoring in geometrically confined systems.