Femtosecond Laser-Induced, Nanoparticle-Embedded Periodic Surface Structures on Crystalline Silicon for Reproducible and Multi-utility SERS Platforms.

Fabrication of reproducible and versatile surface-enhanced Raman scattering (SERS) substrates is crucial for real-time applications such as explosive detection for human safety and biological imaging for cancer diagnosis. However, it still remains a challenging task, even after several methodologies were developed by various research groups, primarily due to (a) a lack of consistency in detection of a variety of molecules (b) cost-effectiveness of the SERS substrates prepared, and (c) byzantine preparation procedures, etc. Herein, we establish a procedure for preparing reproducible SERS-active substrates comprised of laser-induced nanoparticle-embedded periodic surface structures (LINEPSS) and metallization of silicon (Si) LINEPSS. LINEPSS were fabricated using the technique of femtosecond laser ablation of Si in acetone. The versatile SERS-active substrates were then achieved by two ways, including the drop casting of silver (Ag)/gold (Au) nanoparticles (NPs) on Si LINEPSS and Ag plating on the Si LINEPSS structures. By controlling the LINEPSS grating periodicity, the effect of plasmonic nanoparticles/plasmonic plating on the Si NPs embedded periodic surface structures enormously improved the SPR strength, resulting in the consistent and superior Raman enhancements. The reproducible SERS signals were achieved by detecting the molecules of Methylene Blue (MB), 2,4-dinitrotoluene (DNT), and 5-amino-3-nitro-l,2,4-triazole (ANTA). The SERS signal strength is determined by the grating periodicity, which, in turn, is determined by the input laser fluence. The SERS-active platform with grating periodicity of 130 ± 10 nm and 150 ± 5 nm exhibited strong Raman enhancements of ∼108 for MB and ∼107 for ANTA molecules, respectively, and these platforms are demonstrated to be capable, even for multiple usages.

Self-Assembly of "Chalcone" Type Push-Pull Dye Molecules into Organic Single Crystalline Microribbons and Rigid Microrods for Vis/NIR Range Photonic Cavity Applications.

A novel supramolecular fluorescent donor-acceptor type dye molecule, (2E,4E)-1-(2-hydroxyphenyl)-5-(pyren-1-yl)penta-2,4-dien-1-one (HPPD) self-assembles in a mixture of ethanol/chloroform through intermolecular π-π stacking (distance ca. 3.384 Å) to form J-aggregated single-crystalline microribbons displaying Fabry-Pèrot (F-P) type visible-range optical resonance. The corresponding borondifluoride dye (HPPD-BF), with a reduced HOMO-LUMO gap, self-assembles into crystalline microrods acting as an F-P type resonator in the near-infrared (NIR) range.

Single-particle to single-particle transformation of an active type organic µ-tubular homo-structure photonic resonator into a passive type hetero-structure resonator.

Self-assembled hexagonal organic submicrotubes, upon electronic excitation with an UV laser, display an active type polarized whispering gallery mode (WGM) resonance in the visible (Vis) range (400-600 nm). Due to the photonic cavity effect the tubes show fluorescence (FL) signal intensity 5× greater than the corresponding powder state. Furthermore, the same tubes, which are passive to a visible laser, produce yellow-orange emitting carbonaceous lumps when burnt with an intense laser beam (42 mW) forming a chemically binary heterogeneous structure. The hetero-structure upon excitation with a visible laser at the passive tubular part showed emission in the Vis-Near infrared (NIR) range (500-800 nm) with WGMs thus producing a passive/active type hetero-structure photonic resonator.

Visible-Near-Infrared Range Whispering Gallery Resonance from Photonic µ-Sphere Cavities Self-Assembled from a Blend of Polystyrene and Poly[4,7-bis(3-octylthiophene-2-yl)benzothiadiazole-co-2,6-bis(pyrazolyl)pyridine] Coordinated to Tb(acac)3.

A novel red emitting copolymer (P1) was prepared (Mn ∼ 10.7 kDa) by copolymerizing tridentate ligand, namely 2,6-bis(pyrazolyl)pyridine (BPP) with 4,7-bis(2-ethynyl-5-thienyl)-2,1,3-benzothiadiazole. This copolymer readily formed an orange yellow emitting metal containing conjugated polymer (P1.Tb) with Tb(acac)3. Further, a judicial blend of P1.Tb with polystyrene and its subsequent self-assembly in THF/water produced microspheres with smooth surface area. Interestingly, continuous wave laser excitation of a single microsphere displayed whispering-gallery-mode (WGM) resonance modes over a broad wavelength range covering visible (Vis) and near-infrared (NIR) regions (0.550-0.875 µm). The estimated Q factor was up to 700, which is very high for a metal containing conjugated polymer (MCCP)-based optical gain medium.

Planar active organic waveguide and wavelength filter: self-assembled meso-tetratolylporphyrin hexagonal nanosheet.

We have fabricated nearly monodispersed nanocrystalline sheet waveguides from a well-known red emitting meso-tetratolylporphyrin molecule (1) by following a bottom-up solvent assisted self-assembly technique. The nano-sheets thickness is in the range of 110-180 nm. Localized laser illumination showed excitation position dependent exciton polariton (653 and 719 nm) propagation behavior of the sheets. The spatially resolved fluorescence spectra of the sheets showed optical modes at the input and output points, indicating cavity effect. Additionally, because of the reabsorption of the 653 nm emission, the nanosheets also act as wave length filter by cutting off the 653 nm photons from reaching the output end.