While silver and gold have been the dominant plasmonic metals used for surface-enhanced Raman spectroscopy (SERS) since the field’s inception. We argue that virtually any metal, when appropriately nanostructured as a grating, has the potential to be an efficient SERS substrate. This conclusion provides the basis for making SERS a general tool for studying surface processes and catalysis and allows SERS substrates to be routinely based on earth-abundant, low-cost, and chemically interesting metals. We illustrate the above premise by producing highly performing SERS substrates using aluminum, nickel, and copper in addition to silver and gold as benchmarks. All five metals were found to yield high SERS intensities. The approximately three orders enhancement variation among the five substrates based on differing metals is ascribed mainly to local field effects associated with individual grating elements. This conclusion is supported by local field calculations. This suggests that the largest contribution to the enhancement is a (radiative) nonlocal grating-based (plasmonic) effect which is approximately equal for all of the gratings we studied regardless of metal from which they were fabricated, so long as the structural details of the gratings were kept constant.

Papaverine is a non-narcotic alkaloid found endemically and uniquely in the latex of the opium poppy. It is normally refined out of the opioids that the latex is typically collected for, hence its presence in a sample is strong prima facie evidence that the carrier from whom the sample was collected is implicated in the mass cultivation of poppies or the collection and handling of their latex. We describe an analysis technique combining surface-enhanced Raman spectroscopy (SERS) with microfluidics for detecting papaverine at low concentrations and show that its SERS spectrum has unique spectroscopic features that allows its detection at low concentrations among typical opioids. The analysis requires approximately 2.5 min from sample loading to results, which is compatible with field use. The weak acid properties of papaverine hydrochloride were investigated, and Raman bands belonging to the protonated and unprotonated forms of the isoquinoline ring of papaverine were identified.

Surface-enhanced Raman spectroscopy (SERS) and related spectroscopies are powered primarily by the concentration of the electromagnetic (EM) fields associated with light in or near appropriately nanostructured electrically-conducting materials, most prominently, but not exclusively high-conductivity metals such as silver and gold. This field concentration takes place on account of the excitation of surface-plasmon (SP) resonances in the nanostructured conductor. Optimizing nanostructures for SERS, therefore, implies optimizing the ability of plasmonic nanostructures to concentrate EM optical fields at locations where molecules of interest reside, and to enhance the radiation efficiency of the oscillating dipoles associated with these molecules and nanostructures. This review summarizes the development of theories over the past four decades pertinent to SERS, especially those contributing to our current understanding of SP-related SERS. Special emphasis is given to the salient strategies and theoretical approaches for optimizing nanostructures with hotspots as efficient EM near-field concentrating and far-field radiating substrates for SERS. A simple model is described in terms of which the upper limit of the SERS enhancement can be estimated. Several experimental strategies that may allow one to approach, or possibly exceed this limit, such as cascading the enhancement of the local and radiated EM field by the multiscale EM coupling of hierarchical structures, and generating hotspots by hybridizing an antenna mode with a plasmonic waveguide cavity mode, which would result in an increased local field enhancement, are discussed. Aiming to significantly broaden the application of SERS to other fields, and especially to material science, we consider hybrid structures of plasmonic nanostructures and other material phases and strategies for producing strong local EM fields at desired locations in such hybrid structures. In this vein, we consider some of the numerical strategies for simulating the optical properties and consequential SERS performance of particle-on-substrate systems that might guide the design of SERS-active systems. Finally, some current theoretical attempts are briefly discussed for unifying EM and non-EM contribution to SERS.

Plasmonic nanosystems can enhance photochemical processes taking place in their neighborhood on account of several plasmonically mediated processes, among them: (i) the enhancement of the optical fields in the vicinity of the nanosystem and (ii) the intervention of energetic electrons and/or holes in the redox chemistry of nearby molecules pursuant to plasmon excitation and decay. We describe a series of experiments in which tetrachloroplatinate anions are reduced to zerovalent Pt at the surface of gold nanoparticles and nanoparticle assemblies. We demonstrate that the spatial pattern of deposited Pt cannot be understood in terms of enhanced fields alone but likely involves hot electrons whose momenta are initially aligned with the electric vector of the polarized light used to excite plasmons but become randomized on account of electron–electron interactions and scattering within the metallic nanoparticles before the electrons’ energy is substantially thermalized. These conclusions are supported by numerical computations of the local electromagnetic fields scattered by gold nanoparticles, using a finite element approach. SERS measurements, carried out concurrently with the photoreduction, suggest that PtO2 is at least one of the oxidation products formed in the oxidation reaction(s) countervailing the above reduction reaction.

Gratings have been widely investigated both theoretically and experimentally as surface-enhanced Raman spectroscopy (SERS) substrates, exhibiting, under appropriate circumstances, increased far-field extinctions and near-field intensities over those of an appropriately equivalent number of isolated particles. When the grating order transitions from evanescent to radiative, narrow resonance peaks are observed in the extinction spectrum whose properties can be manipulated by controlling the grating’s geometric parameters. Here we report the application of the architectural principles of grating fabrication using a square two-dimensional array of gold-coated nanostructures that achieves SERS enhancements of 107 uniformly over areas of square centimeters. The high-performance grating substrates were fabricated using commonly available foundry-based techniques that have been chosen for their applicability to large-scale wafer processing. Additionally, we restricted ourselves to a parametric regime that optimizes SERS performance in a repeatable and reproducible manner.Keywords: chemical and biochemical sensing; nanogratings; plasmonic substrate; SERS substrate; Surface-enhanced Raman spectroscopy

Size-selected Ag clusters in the range Ag3–Ag50 were prepared by sputtering a silver substrate, mass-selecting Ag cation clusters using a Wien filter, neutralizing and matrix-isolating them at cryogenic temperatures in solid CO. The Raman spectra of the resulting silver-cluster carbonyls were recorded using excitation wavelengths in the range 457.9 to 514.5 nm. For Ag30 and Ag50, the “adsorbed” carbon monoxide (which we estimated to number ∼25 and ∼40, respectively) gave rise to broad Raman bands centered at ∼2110 cm–1. Because both the metal cluster and the CO density were measured quantitatively, a good estimate was computed for the increase in the Raman scattering cross-section per CO molecule adsorbed on the silver particle. For Ag50 and 457.9 nm laser excitation, an enhancement of ∼1850 was measured, which dropped to ∼1350 at 514.5 nm excitation. For Ag30 (and 457.9 nm excitation) the enhancement was ∼530. The enhancements of Ag3, Ag5, and Ag9 were too low to measure accurately (i.e., <10). Extrapolating the enhancements obtained with blue and green wavelengths to the “plasmonic” band center, which for an Ag50 cluster is expected to be at ∼370 nm, and assuming the excitation band to be a Lorentzian with a fwhh of 0.8 eV, the maximum Raman enhancement per CO ligand in Ag50CO40 was estimated to be ∼12000, in good agreement with computed results using a time-dependent density functional quantum calculation, carried out on a Ag20 cluster complex by Jensen et al. (Jensen et al. Size-Dependence of the Enhanced Raman Scattering of Pyridine Adsorbed on Agn (n = 2–8, 20) Clusters. J. Phys. Chem. C 2007, 111, 4756–4764).

The optical resonances of plasmonic nanostructures depend critically on the geometrical details of the absorber. We show that this unique property of plasmons can potentially be used to create panchromatic absorbers covering most of the useful solar spectrum, by measuring the light-to-hydrogen conversion capabilities of a series multielectrode photocatalytic devices, based on functionalized gold nanorods of appropriately chosen aspect ratios. Judiciously combining nanorods of various aspect ratios almost doubles the H2 production of the device over what is optimally possible with a device using gold nanorods of a single aspect ratio (all other key parameters being equal). The estimated quantum efficiency (absorbed photons-to-hydrogen) averaged over the entire solar spectrum of the best performing plasmonic multielectrode array was approximately 0.1%, and the measured H2 production rate for all of the devices was found to be approximately proportional to the hot electron generation. The device was monitored continuously for over 200 hr of operation without measurable diminution in the rate.

Surface enhanced Raman spectroscopy (SERS) is a powerful analytical technique that has been proposed as a substitute for fluorescence for biological imaging and detection but is not yet commercially utilized. The reason lies primarily in the lower intensity and poor reproducibility of most metal nanoparticle-based tags as compared to their fluorescence-based counterparts. Here, using a technique that scrupulously preserves the same number of dye molecules in both the SERS and fluorescence measurements, we show that SERS-based biotags (SBTs) with highly reproducible optical properties can be nanoengineered such that their brightness is at least equal to that of fluorescence-based tags.

Surface-enhanced Raman spectroscopy (SERS) is a useful technique for probing analyte–noble metal interactions and determining thermodynamic properties such as their surface reaction equilibrium constants and binding energies. In this study, we measure the binding equilibrium constants and Gibbs free energy of binding for a series of nitrogen-containing aromatic molecules adsorbed on Klarite substrates. A dual Langmuir dependence of the SERS intensity on concentration was observed for the six species studied, indicating the presence of at least two different binding energies. We relate the measured binding energies to the previously described SERS enhancement value (SEV) and show that the SEV is proportional to the traditional SERS enhancement factor G, with a constant of proportionality that is critically dependent on the adsorption equilibrium constant determined from the dual Langmuir isotherm. We believe the approach described is generally applicable to many SERS substrates, both as a prescriptive approach to determining their relative performance and as a probe of the substrate’s affinity for a target adsorbate.Keywords: binding energy; enhancement factor; equilibrium constant; Langmuir isotherm; SERS;

Reliable identification and collection of cells from bodily fluids is of growing interest for monitoring patient response to therapy and for early detection of disease or its recurrence. We describe a detection platform that combines microfluidics with surface-enhanced Raman spectroscopy (SERS) for the identification of individual mammalian cells continuously flowing in a microfluidics channel. A mixture of cancerous and noncancerous prostate cells was incubated with SERS biotags (SBTs) developed and synthesized by us, then injected into a flow-focused microfluidic channel, which forces the cells into a single file. The spectrally rich SBTs are based on a silver nanoparticle dimer core labeled with a Raman-active small reporter molecule paired with an affinity biomolecule, providing a unique barcode whose presence in a composite SERS spectrum can be deconvoluted. Individual cancer cells passing through the focused laser beam were correctly identified among a proportionally larger number of other cells by their Raman signatures. We examine two deconvolution strategies: principal component analysis and classical least-squares. The deconvolution strategies are used to unmix the overall spectrum to determine the relative contributions between two SBT barcodes, where one SBT barcode indicates neuropilin-1 overexpression, while a second SBT barcode is more universal and indicates unspecific binding to a cell’s membrane. Highly reliable results were obtained for all of the cell mixture ratios tested, the lowest being 1 in 100 cells.Keywords: cancer diagnostics; chemometrics; microfluidics; multiplexed; SERS;

The conversion of sunlight into electricity by photovoltaics is currently a mature science and the foundation of a lucrative industry. In conventional excitonic solar cells, electron–hole pairs are generated by light absorption in a semiconductor and separated by the “built in” potential resulting from charge transfer accompanying Fermi-level equalization either at a p–n or a Schottky junction, followed by carrier collection at appropriate electrodes. Here we report a stable, wholly plasmonic photovoltaic device in which photon absorption and carrier generation take place exclusively in the plasmonic metal. The field established at a metal–semiconductor Schottky junction separates charges. The negative carriers are high-energy (hot) electrons produced immediately following the plasmon’s dephasing. Some of the carriers are energetic enough to clear the Schottky barrier or quantum mechanically tunnel through it, thereby producing the output photocurrent. Short circuit photocurrent densities in the range 70–120 μA cm–2 were obtained for simulated one-sun AM1.5 illumination with devices based on arrays of parallel gold nanorods, conformally coated with 10 nm TiO2 films and fashioned with a Ti metal collector. For the device with short circuit currents of 120 μA cm–2, the internal quantum efficiency is ∼2.75%, and its wavelength response tracks the absorption spectrum of the transverse plasmon of the gold nanorods indicating that the absorbed photon-to-electron conversion process resulted exclusively in the Au, with the TiO2 playing a negligible role in charge carrier production. Devices fabricated with 50 nm TiO2 layers had open-circuit voltages as high as 210 mV, short circuit current densities of 26 μA cm–2, and a fill factor of 0.3. For these devices, the TiO2 contributed a very small but measurable fraction of the charge carriers.Keywords: gold nanorods; photovoltaics; Schottky barrier; surface plasmons; TiO2

That a nanoparticle (NP) (for example of gold) residing above a gold mirror is almost as effective a surface enhanced Raman scattering (SERS) substrate (when illuminated with light of the correct polarization and wavelength) as two closely coupled gold nanoparticles has been known for some time.(1, 2) The NP-overmirror (NPOM) configuration has the valuable advantage that it is amenable to top-down fabrication. We have fabricated a series of Au-NPOM substrates with varying but thin atomic layer-deposited oxide spacer and measured the SERS enhancement as a function of spacer thickness and angle of incidence (AOI). These were compared with high-quality finite-difference time-domain calculations, which reproduce the observed spacer thickness and AOI dependences faithfully. The SERS intensity is expected to be strongly affected by the AOI on account for the fact that the hot spot formed in the space between the NP and the mirror is most efficiently excited with an electromagnetic field component that is normal to the surface of the mirror. Intriguingly we find that the SERS intensity maximizes at ∼60° and show that this is due to the coherent superposition of the incident and the reflected field components.(3) The observed SERS intensity is also shown to be very sensitive to the dielectric constant of the oxide spacer layer with the most intense signals obtained when using a low dielectric constant oxide layer (SiO2).

We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO2, forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.

Arrays of periodically disposed silver nanowires embedded in alumina were shown to be capable of conducting plasmons excited by laser illuminating one end of the array to its opposite end where surface-enhanced Raman of molecules resident among the tips of the nanowires was excited. The SERS signals, in turn, excited plasmons which propagated back to the originally illuminated ends of the nanowires where they emitted light signals that were collected and spectroscopically dispersed, in essence creating a sensor capable of exciting and collecting SERS remotely. For nanowire arrays with interwire gaps of ∼11 nm and lengths of ∼3.3 μm (i.e., after a ∼6.6 μm round trip) the SERS signals obtained by remote sensing were rather strong, ∼5% the intensity of those obtained by exciting the molecules resident among the nanowire tips directly.

Metal ion carboxylato complexes possess ion-specific carboxylate Raman bands. Using this attribute we follow the chromatographic separation of a microliter aliquot of an initially equimolar solution of Pb2+ and Hg2+ using the surface-enhanced Raman spectroscopy spectra of their carboxylato complexes as unique identifiers. A glass capillary whose interior is lined with a dense layer of gold nanoparticles treated with 4-mercaptobenzoic acid simultaneously acts as a separation medium and an efficient SERS reporter of the step-by-step separation process. The observed adsorption−desorption equilibrium along the capillary is shown to conform with theory. Although Hg2+ complexes with COO− much more strongly than Pb2+, it is the Pb2+ that survives the separation process as the sole surface species. We show that this is because so much mercury is taken out of solution during early separation steps that the surface equilibrium is ultimately driven toward adsorbed Pb2+.

A fruitful paradigm in the development of low-cost and efficient photovoltaics is to dope or otherwise photosensitize wide band gap semiconductors in order to improve their light harvesting ability for light with sub-band-gap photon energies.1–8 Here, we report significant photosensitization of TiO2 due to the direct injection by quantum tunneling of hot electrons produced in the decay of localized surface-plasmon polaritons excited in gold nanoparticles (AuNPs) embedded in the semiconductor (TiO2). Surface plasmon decay produces electron–hole pairs in the gold.9–15 We propose that a significant fraction of these electrons tunnel into the semiconductor’s conduction band resulting in a significant electron current in the TiO2 even when the device is illuminated with light with photon energies well below the semiconductor’s band gap. Devices fabricated with (nonpercolating) multilayers of AuNPs in a TiO2 film produced over 1000-fold increase in photoconductance when illuminated at 600 nm over what TiO2 films devoid of AuNPs produced. The overall current resulting from illumination with visible light is ∼50% of the device current measured with UV (ℏω > Eg band gap) illumination. The above observations suggest that plasmonic nanostructures (which can be fabricated with absorption properties that cover the full solar spectrum) can function as a viable alternative to organic photosensitizers for photovoltaic and photodetection applications.

A multiplexed, ratiometric method is described that can confidently distinguish between cancerous and noncancerous epithelial prostate cells in vitro. The technique is based on bright surface-enhanced resonance Raman scattering (SERRS) biotags (SBTs) infused with unique Raman reporter molecules, and carrying cell-specific peptides. Two sets of SBTs were used. One targets the neuropilin-1 (NRP-1) receptors of cancer cells through the RPARPAR peptide. The other functions as a positive control (PC) and binds to both noncancerous and cancer cells through the HIV-derived TAT peptide. Point-by-point 2D Raman maps of the spatial distribution of the two tags were constructed with subcellular resolution from cells simultaneously incubated with the two sets of SBTs. Averaging the SERRS signal over a given cell yielded an NRP/PC ratio from which a robust quantitative measure of the overexpression of the NRP-1 by the cancer cell line was extracted. The use of a local, on-cell reference produces quantitative, statistically robust measures of overexpression independent of such sources of uncertainty as variations in the location of the focal plane, the local cell concentration, and turbidity.

A bifunctional adenosine-sensitive double-stranded DNA aptamer was used to create and control a surface-enhanced Raman spectroscopy (SERS) hot spot between a bulk Au surface and a gold nanoparticle (Au NP) attached to the aptamer via a biotin−avidin linkage. The Au NP was decorated with 4-aminobenzenethiol (4-ABT), a Raman reporter molecule. In the presence of adenosine, the target molecule, the SERS spectrum of 4-ABT increased in intensity by (concentration-dependent) factors as large as ∼4; in situ, atomic force microscopy imaging showed the mean height of the Au NP-bearing aptamer to decrease by ∼5 nm consistent with the observed SERS intensity change. Because the aptamer’s geometrical change is induced by one or two molecules, while the resulting SERS intensity changes involve many reporter molecules residing in the modified hot spot, the aptamer amplifies the SERS effect.

Photovoltaic devices based on organic semiconductors require charge-separating networks (bulk heterojunctions) for optimal performance. Here we report on the fabrication of organic−inorganic photovoltaic devices with tailored (n-type) CdSe nanorod arrays aligned perpendicularly to the substrate. The nanorod lengths varied from 58 ± 12 to 721 ± 15 nm, while the diameters and inter-rod spacings were kept constant at 89.5 ± 7.5 and 41.3 ± 9.9 nm, respectively. Short-circuit densities improved linearly with nanorod length, resulting in power conversion efficiencies of up to 1.38% for cells with nanorods 612 ± 46 nm long. Notably, the cell’s efficiency was dominated by exciton generation in the CdSe nanorods.Keywords: hybrid; nanorod; organic; photovoltaic; porous aluminum oxide

Surface-enhanced Raman spectroscopy (SERS) and related spectroscopies are powered primarily by the concentration of the electromagnetic (EM) fields associated with light in or near appropriately nanostructured electrically-conducting materials, most prominently, but not exclusively high-conductivity metals such as silver and gold. This field concentration takes place on account of the excitation of surface-plasmon (SP) resonances in the nanostructured conductor. Optimizing nanostructures for SERS, therefore, implies optimizing the ability of plasmonic nanostructures to concentrate EM optical fields at locations where molecules of interest reside, and to enhance the radiation efficiency of the oscillating dipoles associated with these molecules and nanostructures. This review summarizes the development of theories over the past four decades pertinent to SERS, especially those contributing to our current understanding of SP-related SERS. Special emphasis is given to the salient strategies and theoretical approaches for optimizing nanostructures with hotspots as efficient EM near-field concentrating and far-field radiating substrates for SERS. A simple model is described in terms of which the upper limit of the SERS enhancement can be estimated. Several experimental strategies that may allow one to approach, or possibly exceed this limit, such as cascading the enhancement of the local and radiated EM field by the multiscale EM coupling of hierarchical structures, and generating hotspots by hybridizing an antenna mode with a plasmonic waveguide cavity mode, which would result in an increased local field enhancement, are discussed. Aiming to significantly broaden the application of SERS to other fields, and especially to material science, we consider hybrid structures of plasmonic nanostructures and other material phases and strategies for producing strong local EM fields at desired locations in such hybrid structures. In this vein, we consider some of the numerical strategies for simulating the optical properties and consequential SERS performance of particle-on-substrate systems that might guide the design of SERS-active systems. Finally, some current theoretical attempts are briefly discussed for unifying EM and non-EM contribution to SERS.

A plasmonic liquid junction photovoltaic cell with greatly improved power conversion efficiency is described. When illuminated with simulated sunlight, the device (Au–TiO2/V3+(0.018 M), V2+(0.182 M)/Pt) reproducibly and sustainably produces an VOC of 0.50 V and a JSC of 0.5 mA cm−2, corresponding to a power conversion efficiency of 0.095%.