Characterization of novel Ag on TiO2 films for surface-enhanced Raman scattering

Novel Ag on TiO₂ films are generated by semiconductor photocatalysis and characterized by ultraviolet-visible (UV/Vis) spectroscopy, scanning electron microscopy (SEM), and atomic force microscopy (AFM), as well as assessed for surface-enhanced Raman scattering (SERS) activity. The nature and thickness of the photodeposited Ag, and thus the degree of SERS activity, is controlled by the time of exposure of the TiO₂ film to UV light. All such films exhibit the optical characteristics (λ_max ≅ 390 nm) of small (<20 nm) Ag particles, although this feature becomes less prominent as the film becomes thicker. The films comprise quite large (>40 nm) Ag islands that grow and merge with increasing levels of Ag photodeposition. Tested with a benzotriazole dye probe, the films are SERS active, exhibiting activity similar to that of 6-nm-thick vapordeposited films. The Ag/TiO₂ films exhibit a lower residual standard deviation (∼25%) compared with Ag vapor-deposited films (∼45%), which is, however, still unacceptable for quantitative work. The sample-to-sample variance could be reduced significantly (<7%) by spinning the film during the SERS measurement. The Ag/TiO₂ films are mechanically robust and resistant to removal and damage by scratching, unlike the Ag vapor-deposited films. The Ag/TiO₂ films also exhibit no obvious loss of SERS activity when stored in the dark under otherwise ambient conditions. The possible extension of this simple, effective method of producing Ag films for SERS, to metals other than Ag and to semiconductors other than TiO₂, is briefly discussed. 

Label-free detection of nanomolar unmodified single- and double-stranded dna by using surface-enhanced raman spectroscopy on Ag and Au colloids

Unlabelled single- and double-stranded DNA (ssDNA and dsDNA, respectively) has been detected at concentrations =10-9?M by surface-enhanced Raman spectroscopy. Under appropriate conditions the sequences spontaneously adsorbed to the surface of both Ag and Au colloids through their nucleobases; this allowed highly reproducible spectra with good signal-to-noise ratios to be recorded on completely unmodified samples. This eliminated the need to promote absorption by introducing external linkers, such as thiols. The spectra of model ssDNA sequences contained bands of all the bases present and showed systematic changes when the overall base composition was altered. Initial tests also showed that small but reproducible changes could be detected between oligonucleotides with the same bases arranged in a different order. The spectra of five ssDNA sequences that correspond to different strains of the Escherichia coli bacterium were found to be sufficiently composition-dependent so that they could be differentiated without the need for any advanced multivariate data analysis techniques.

Surface-Enhanced Raman Scattering from Metallic Nanostructures: Bridging the Gap between the Near-Field and Far-Field Responses

We present here a detailed study of the complex relationship between the electromagnetic near-field and far-field responses of "real" nanostructured metallic surfaces. The near-field and far-field responses are specified in terms of (spectra of) the surface-enhanced Raman-scattering enhancement factor (SERS EF) and optical extinction, respectively. First, it is shown that gold nanorod- and nanotube-array substrates exhibit three distinct localized surface plasmon resonances (LSPRs): a longitudinal, a transverse, and a cavity mode. The cavity mode simultaneously has the largest impact on the near-field behavior (as observed through the SERS EF) and the weakest optical interaction: It has a "near-field-type" character. The transverse and longitudinal modes have a significant impact on the far-field behavior but very little impact on SERS: They have a "far-field-type" character. We confirm the presence of the cavity mode using a combination of SERS EF spectra, electron microscopy, and electromagnetic modeling and thus clearly illustrate and explain the (lack of) correlation between the SERS EF spectra and the optical response in terms of the contrasting character of the three LSPRs. In doing so, we experimentally demonstrate that, for a surface that supports multiple LSPRs, the near-field and far-field properties can in fact be tuned almost independently. It is further demonstrated that small changes in geometrical parameters that tune the spectral location of the LPSRs can also drastically influence the character of these modes, resulting in certain unusual behavior, such as the far-field resonance redshift as the near-field resonance blueshifts. DOI: 10.1103/PhysRevX.3.011001

Highly Sensitive, Uniform, and Reproducible Surface-Enhanced Raman Spectroscopy from Hollow Au-Ag Alloy Nanourchins

A hierarchical nanoparticle strategy to simultaneously gain super Raman signal amplification, high uniformity, and reproducibility is presented. Using hollow Au-Ag alloy nanourchins, an ultrahigh sensitivity, e.g., down to 1 fM concentrations for DEHP molecule is obtained. A small standard deviation of <10% is achieved by simply dropping and evaporating sub-100 nm nanourchins onto a substrate.

Detection of Low-Concentration Contaminants in Solution by Exploiting Chemical Derivatization in Surface-Enhanced Raman Spectroscopy

INFLUENCE OF METAL GRAIN-SIZE ON SURFACE-ENHANCED RAMAN-SCATTERING

The surface roughness of nominally smooth and of randomly roughened thin silver films is characterized using scanning tunneling microscopy and the metal grain size is assessed using transmission electron microscopy. On each type of substrate used, glass or CaF2-roughened glass, the silver films are deposited either very slowly (approximately 0.15 nm s-1) or quite quickly (approximately 2.0 nm s-1). Only silver films deposited on CaF2-roughened glass yield measurable surface-enhanced Raman signals for benzoic acid; the enhancement is brought about by surface field amplification due to the excitation of delocalized surface-plasmon polaritons. However, the surface-enhanced Raman signals obtained from the slow-deposited silver films are significantly better (by about a factor of 3) than those obtained from the fast-deposited silver films on a given CaF2-roughened substrate. The explanation of this observation does not lie with different surface roughness; both types of film yield closely similar data on the scanning tunneling microscope. Rather, it is suggested that the relatively small grain size of the fast-deposited silver films leads to increased elastic scattering of surface-plasmon polaritons at the grain boundaries, with a consequent increase of internal damping. This results in a reduction of the scattered Raman signal.

Preaggregated Ag Nanoparticles in Dry Swellable Gel Films for Off-the-Shelf Surface-Enhanced Raman Spectroscopy

Large, thin (50 mu m) dry polymer sheets containing numerous surface-enhanced Raman spectroscopy (SERS) active Ag nanopartide aggregates have been prepared by drying aqueous mixtures of hydroxyethylcelloulose (HEC) and preaggregated Ag colloid in 10 x 10 cm molds. In these dry films, the particle aggregates are protected from the environment during storage and are easy to handle; for example, they can be cut to size with scissors. When in use, the highly swellable HEC polymer allowed the films to rapidly absorb aqueous analyte solutions while simultaneously releasing the Ag nanoparticle aggregates to interact with the analyte and generate large SERS signals. Either the films could be immersed in the analyte solution or 5 mu L droplets were applied to the surface; in the latter method, the local swelling caused the active area to dome upward, but the swollen film remained physically robust and could be handled as required. Importantly, encapsulation and release did not significantly compromise the SERS performance of the colloid; the signals given by the swollen films were similar to the very high signals obtained from the parent citrate-reduced colloid and were an order of magnitude larger than a commercially available nanoparticle substrate. These "Poly-SERS" films retained 70% of their SERS activity after being stored for 1 year in air. The films were sufficiently homogeneous to give a standard deviation of 3.2% in the absolute signal levels obtained from a test analyte, primarily due to the films' ability to suppress "coffee ring" drying marks, which meant that quantitative analysis without an internal standard was possible. The majority of the work used aqueous thiophenol as the test analyte; however, preliminary studies showed that the Poly-SERS films could also be used with nonaqueous solvents and for a range of other analytes including theophylline, a therapeutic drug, at a concentration as low as 1.0 x 10(-5) mol dm(-3) (1.8 mg/dm(3)), well below the sensitivity required for theophylline monitoring where the target range is 10-20 mg/dm(3).

SURFACE ENHANCED RAMAN-SCATTERING FROM MILDLY ROUGHENED SURFACES - VARIATION OF SIGNAL WITH METAL GRAIN-SIZE

The intensity of surface enhanced Raman scattering from benzoic acid derivatives on mildly roughened, thermally evaporated Ag films shows a remarkably strong dependence on metal grain size. Large grained (slowly deposited) films give a superior response, by up to a factor of 10, to small grained (quickly deposited) films, with films of intermediate grain size yielding intermediate results. The optical field amplification underlying the enhancement mechanism is due to the excitation of surface plasmon polaritons (SPPs). Since surface roughness characteristics, as determined by STM, remain relatively constant as a function of deposition rate, it is argued that the contrast in Raman scattering is due to differences in elastic grain boundary scattering of SPPs (leading to different degrees of internal SPP damping), rather than differences in the interaction of SPPs with surface inhomogeneities.

Simple preparation of positively charged silver nanoparticles for detection of anions by surface-enhanced Raman spectroscopy

Modification of citrate and hydroxylamine reduced Ag colloids with thiocholine bromide, a thiol functionalized quaternary ammonium salt, creates particles where the zeta potential is switched from the normal values of ca. -50 mV to ca. + 50 mV. These colloids are stable but can be aggregated with metal salts in much the same way as the parent colloids. They are excellent SERS substrates for detection of anionic targets since their positive zeta potentials promote adsorption of negatively charged ions. This is important because the vast majority of published SERS studies involve cationic or neutral targets. Moreover, the fact that the modifier is a quaternary ammonium ion means that the negative surface charge is maintained even at alkaline pH. The modified colloids can be used to detect compounds which cannot be detected using conventional negatively-charged citrate or hydroxylamine reduced metal nanoparticles, for example the detection limit was 5.0 x 10(-5) M for perchlorate and

Surface-Enhanced Raman Spectroscopy as a Probe of the Surface Chemistry of Nanostructured Materials

Surface-enhanced Raman spectroscopy (SERS) is now widely used as a rapid and inexpensive tool for chemical/biochemical analysis. The method can give enormous increases in the intensities of the Raman signals of low-concentration molecular targets if they are adsorbed on suitable enhancing substrates, which are typically composed of nanostructured Ag or Au. However, the features of SERS that allow it to be used as a chemical sensor also mean that it can be used as a powerful probe of the surface chemistry of any nanostructured material that can provide SERS enhancement. This is important because it is the surface chemistry that controls how these materials interact with their local environment and, in real applications, this interaction can be more important than more commonly measured properties such as morphology or plasmonic absorption. Here, the opportunity that this approach to SERS provides is illustrated with examples where the surface chemistry is both characterized and controlled in order to create functional nanomaterials.

Swellable polymer films containing Au nanoparticles for point-of-care therapeutic drug monitoring using surface-enhanced Raman spectroscopy

Large (10 × 10 cm) sheets of surface-enhanced Raman spectroscopy (SERS) active polymer have been prepared by stabilising metal nanoparticle aggregates within dry hydroxyethylcellulose (HEC) films. In these films the aggregates are protected by the polymer matrix during storage but in use they are released when aqueous analyte droplets cause the films to swell to their gel form. The fact that these "Poly-SERS" films can be prepared in bulk but then cut to size and stored in air before use means that they provide a cost effective and convenient method for routine SERS analysis. Here we have tested both Ag and Au Poly-SERS films for use in point-of-care monitoring of therapeutic drugs, using phenytoin as the test compound. Phenytoin in water could readily be detected using Ag Poly-SERS films but dissolving the compound in phosphate buffered saline (PBS) to mimic body fluid samples caused loss of the drug signal due to competition for metal surface sites from Cl^- ions in the buffer solution. However, with Au Poly-SERS films there was no detectable interference from Cl^- and these materials allowed phenytoin to be detected at 1.8 mg L^-1, even in PBS. The target range of detection of phenytoin in therapeutic drug monitoring is 10-20 mg L^-1. With the Au Poly-SERS films, the absolute signal generated by a given concentration of phenytoin was lower for the films than for the parent colloid but the SERS signals were still high enough to be used for therapeutic monitoring, so the cost in sensitivity for moving from simple aqueous colloids to films is not so large that it outweighs the advantages which the films bring for practical applications, in particular their ease of use and long shelf life.