G. V. Pavan Kumar

Plasmonic nano-architectures for surface enhanced Raman scattering: a review

Surface enhanced Raman scattering (SERS) is an optical spectroscopy technique with single molecule sensitivity and chemical specificity. The electromagnetic enhancement mechanism of SERS is facilitated by the localized surface plasmons of metallic nanostructures utilized in experiments. The magnitude of the local optical field created by the plasmonic nanostructure depends on parameters such as size, shape, morphology, arrangement, and local environment of the nanostructure. By tuning these parameters, electromagnetic hot spots can be created to facilitate ultra-sensitive, subwavelength SERS detection platforms. In recent years, there have been a number of innovations in nanofabrication and synthesis of plasmonic nanostructures. This has led to a variety of plasmonic nano-architectures that can be harnessed for SERS. Recently investigated plasmonic nanostructures in the context of SERS include nanosphere dimers, individual nanocubes, nanotriangular arrays, nano-pyramid shells, individual and assembly of nanorods, nanowires, and nanotips, and some unconventional nano-architectures. Challenges in fundamental and application aspects of SERS remain for future research.

Plasmofluidic single-molecule surface-enhanced Raman scattering from dynamic assembly of plasmonic nanoparticles.

Single-molecule surface-enhanced Raman scattering (SM-SERS) is one of the vital applications of plasmonic nanoparticles. The SM-SERS sensitivity critically depends on plasmonic hot-spots created at the vicinity of such nanoparticles. In conventional fluid-phase SM-SERS experiments, plasmonic hot-spots are facilitated by chemical aggregation of nanoparticles. Such aggregation is usually irreversible, and hence, nanoparticles cannot be re-dispersed in the fluid for further use. Here, we show how to combine SM-SERS with plasmon polariton-assisted, reversible assembly of plasmonic nanoparticles at an unstructured metal-fluid interface. One of the unique features of our method is that we use a single evanescent-wave optical excitation for nanoparticle assembly, manipulation and SM-SERS measurements. Furthermore, by utilizing dual excitation of plasmons at metal-fluid interface, we create interacting assemblies of metal nanoparticles, which may be further harnessed in dynamic lithography of dispersed nanostructures. Our work will have implications in realizing optically addressable, plasmofluidic, single-molecule detection platforms.

Single-Molecule Surface-Enhanced Raman Scattering Sensitivity of Ag-Core Au-Shell Nanoparticles: Revealed by Bi-Analyte Method

Single-molecule surface-enhanced Raman scattering (SM-SERS) is an important application of localized surface plasmons in metallic nanostructures. Conventionally, Ag nanoparticles are used in solution-based SM-SERS experiments, but their usage is limited due to toxicity and oxidation issues. Au nanoparticle solutions are relatively biocompatible and SERS-active, but they do not facilitate large-scale SERS enhancement factors, which is an important prerequisite for SM-SERS. Under such constraints, silver-core gold-shell nanoparticles can be an excellent alternative for SM-SERS. Motivated by this, herein we report on the experimental evidence of SM-SERS sensitivity of Ag-core Au-shell nanoparticles by employing bianalyte method. Additionally, by detecting resonant molecules at femtomolar concentrations, we show that Ag-core Au-shell nanoparticle can be harnessed for ultrasensitive detection of molecules. The provided evidence will further motivate usage of such gold-shell-based bimetallic nanostructures for SM-SERS in biological environments.

Highly tapered pentagonal bipyramidal Au microcrystals with high index faceted corrugation: Synthesis and optical properties

Focusing light at sub-wavelength region opens up interesting applications in optical sensing and imaging beyond the diffraction limit. In the past, tapered Au wires with carved gratings have been employed to achieve nanofocusing. The fabrication process however, is expensive and the obtained wires are polycrystalline with high surface roughness. A chemical synthetic method overcoming these hurdles should be an attractive alternative. Here, we report a method to chemically synthesize Au microcrystals (~10 μm) bearing pentagonal bipyramidal morphology with surface corrugations assignable to high index planes. The method is a single step solid state synthesis at a temperature amenable to common substrates. The microcrystals are tapered at both ends forming sharp tips (~55 nm). Individual microcrystals have been used as pick and probe SERS substrates for a dye embedded in a polymer matrix. The unique geometry of the microcrystal also enables light propagation across its length.

Raman spectra of vibrational and librational modes in methane clathrate hydrates using density functional theory

The sI type methane clathrate hydrate lattice is formed during the process of nucleation where methane gas molecules are encapsulated in the form of dodecahedron (5(12)CH(4)) and tetrakaidecahedron (5(12)6(2)CH(4)) water cages. The characterization of change in the vibrational modes which occur on the encapsulation of CH(4) in these cages plays a key role in understanding the formation of these cages and subsequent growth to form the hydrate lattice. In this present work, we have chosen the density functional theory (DFT) using the dispersion corrected B97-D functional to characterize the Raman frequency vibrational modes of CH(4) and surrounding water molecules in these cages. The symmetric and asymmetric C-H stretch in the 5(12)CH(4) cage is found to shift to higher frequency due to dispersion interaction of the encapsulated CH(4) molecule with the water molecules of the cages. However, the symmetric and asymmetric O-H stretch of water molecules in 5(12)CH(4) and 5(12)6(2)CH(4) cages are shifted towards lower frequency due to hydrogen bonding, and interactions with the encapsulated CH(4) molecules. The CH(4) bending modes in the 5(12)CH(4) and 5(12)6(2)CH(4) cages are blueshifted, though the magnitude of the shifts is lower compared to modes in the high frequency region which suggests bending modes are less affected on encapsulation of CH(4). The low frequency librational modes which are collective motion of the water molecules and CH(4) in these cages show a broad range of frequencies which suggests that these modes largely contribute to the formation of the hydrate lattice.

Plasmon assisted light propagation and Raman scattering hot-spot in end-to-end coupled silver nanowire pairs

Herein, we report on the experimental observation of light propagation and localization capabilities of end-to-end connected silver nanowire (Ag NW) pairs. By exciting the surface plasmon polaritons at one end of Ag NW pair, we observed relatively intense light emission at the junction and weak light emission at the distal end of the pair. To probe the localization of light at nanowire junction, we captured far-field Raman image of an isolated Ag NW pair adsorbed with rhodamine 6 G and observed enhanced Raman scattering at the nanowire junction. Such nanophotonic modules with light propagation and localization capabilities can be harnessed for multiplexed on-chip plasmonics.

Surface-enhanced Raman spectroscopic studies of coactivator-associated arginine methyltransferase 1.

We report, for the first time, the surface-enhanced Raman spectra of an important enzyme, coactivator-associated arginine methyltransferase 1 (CARM1), involved in various biological activities such as tumor suppressor function and stem cell differentiation. We have employed surface-enhanced Raman scattering (SERS) to obtain insight into the structural details of CARM1 by adsorbing it to silver (Ag) nanoparticles. The enzyme retains its activity even after its adsorption onto Ag nanoparticles. We observe strong SERS modes arising from amide vibrations and aromatic ring amino acids. The SERS spectra revealed amide I bands at 1637 cm(-1) and 1666 cm(-1), which arise as a result of the alpha helix of the protein and the polypeptide backbone vibration of a random coil, respectively. In order to confirm the amide vibrations, we have performed SERS on deuterated CARM1, which exhibits a clear red shift in amide band positions. The SERS spectra may provide useful information, which could be harnessed to study the functional interactions of CARM1 with small molecule modulators.

Palladium bridged gold nanocylinder dimer: plasmonic properties and hydrogen sensitivity

Plasmonic nanodimers facilitate electromagnetic hotspots at their gap junction. By loading these gap junctions with nanomaterials, the plasmonic properties of nanodimer can be varied. In this study, we bridged the gap junction of gold (Au) nanocylinder dimer with palladium (Pd), and numerically evaluated the plasmonic properties of the designed nanostructure. We simulated the far-field extinction spectra of Pd bridged Au nanocylinder dimer, and identified the dipole and quadrupole plasmon modes at 839 and 578 nm, respectively. By varying the geometrical parameters of the Pd bridge, we revealed the ability to tune the dipolar plasmon resonance of the bridged dimer. Further, we exploited the hydrogen sensitivity of Pd bridge to harness the bridged-Au dimer as nanoplasmonic hydrogen sensor. Such nano-optical detection platforms have minimal spatial footprint and can be further harnessed for chip-based plasmonic sensing.

Exciton Emission Intensity Modulation of Monolayer MoS 2 via Au Plasmon Coupling

Modulation of photoluminescence of atomically thin transition metal dichalcogenide two-dimensional materials is critical for their integration in optoelectronic and photonic device applications. By coupling with different plasmonic array geometries, we have shown that the photoluminescence intensity can be enhanced and quenched in comparison with pristine monolayer MoS2. The enhanced exciton emission intensity can be further tuned by varying the angle of polarized incident excitation. Through controlled variation of the structural parameters of the plasmonic array in our experiment, we demonstrate modulation of the photoluminescence intensity from nearly fourfold quenching to approximately threefold enhancement. Our data indicates that the plasmonic resonance couples to optical fields at both, excitation and emission bands, and increases the spontaneous emission rate in a double spacing plasmonic array structure as compared with an equal spacing array structure. Furthermore our experimental results are supported by numerical as well as full electromagnetic wave simulations. This study can facilitate the incorporation of plasmon-enhanced transition metal dichalcogenide structures in photodetector, sensor and light emitter applications.

Directional out-coupling of light from a plasmonic nanowire-nanoparticle junction

We experimentally show how a single Ag nanoparticle (NP) coupled to an Ag nanowire (NW) can convert propagating surface plasmon polaritons to directional photons. By employing dual-excitation Fourier microscopy with spatially filtered collection-optics, we show single- and dual-directional out-coupling of light from NW-NP junction for plasmons excited through glass-substrate and air-superstrate. Furthermore, we show NW-NP junction can influence the directionality of molecular-fluorescence emission, thus functioning as an optical antenna. The results discussed herein may have implications in realizing directional single-photon sources and quantum plasmon circuitry.