We demonstrate template-guided self-assembly of gold nanoparticles into ordered arrays of uniform clusters suitable for high-performance SERS on both flat (silicon or glass) chips and an optical fiber faucet. Cluster formation is driven by electrostatic self-assembly of anionic citrate-stabilized gold nanoparticles (~11.6 nm diameter) onto two-dimensionally ordered polyelectrolyte templates realized by self-assembly of polystyrene-block-poly(2-vinylpyridine). A systematic variation is demonstrated for the number of particles (N ≈ 5, 8, 13, or 18) per cluster as well as intercluster separations (S(c) ≈ 37-10 nm). Minimum interparticle separations of <5 nm, intercluster separations of ~10 nm, and nanoparticle densities on surfaces as high as ~7 × 10(11)/in.(2) are demonstrated. Geometric modeling is used to support experimental data toward estimation of interparticle and intercluster separations in cluster arrays. Optical modeling and simulations using the finite difference time domain method are used to establish the influence of cluster size, shape, and intercluster separations on the optical properties of the cluster arrays in relation to their SERS performance. Excellent SERS performance, as evidenced by a high enhancement factor, >10(8) on flat chips and >10(7) for remote sensing, using SERS-enabled optical fibers is demonstrated. The best performing cluster arrays in both cases are achievable without the use of any expensive equipment or clean room processing. The demonstrated approach paves the way to significantly low-cost and high-throughput production of sensor chips or 3D-configured surfaces for remote sensing applications.
We present an inherently reproducible route to realizing high-performance SERS substrates by exploiting a high-throughput top-down/bottom-up fabrication scheme. The fabrication route employs self-assembly of amphiphilic copolymers to create high-resolution molds for nanoimprint lithography (NIL) spanning entire 100 mm Si wafers. The nanoporous polymer templates obtained upon NIL are subjected to galvanic displacement reactions to create gold nanorod arrays. Nanorods are subsequently converted to nanodiscs by thermal annealing. The nanodiscs were found to perform as robust SERS substrates as compared with the nanorods. The SERS performance of these substrates and its generality for catering to diverse molecules is demonstrated through the excellent Raman peak resolution and intensity for three different molecules, exhibiting different interaction modes on surface. Numerical simulations using FDTD shows plasmonic coupling between the particles and also brings out the influence due to size distribution. The approach combines distinct advantages of high-precision and repeatability offered by NIL with low-cost fabrication of high-resolution NIL molds by copolymer self-assembly.
Strong nonlinear absorption is observed in nanocomposite films containing PbS nanocrystals of mean size of 3.3 nm stabilized in a commercial poly(vinyl acetate) glue by a novel and simple chemical route of synthesis. A significant blueshift of the optical absorption edge indicates strong quantum confinement. The mean nanocrystal size was characterized by x-ray diffraction and transmission electron microscopy. The surface structure of nanocrystals is analysed using infrared spectroscopy. The excitonic transitions are probed by photoacoustic spectroscopy and the results are analysed on the basis of theoretical calculations using envelope function formalism. Results of open aperture z-scan experiments suggest a model involving saturable absorption followed by two-photon absorption at a lower concentration while the data for a higher concentration fitted saturable absorption followed by three-photon absorption. Free carrier absorption due to two-photon-assisted excited state absorption appears to be the predominant mechanism of optical nonlinearity.
Stable films containing CdS quantum dots of mean size 3.4 nm embedded in a solid host matrix are prepared using a room temperature chemical route of synthesis. CdS/synthetic glue nanocomposites are characterized using high resolution transmission electron microscopy, infrared spectroscopy, differential scanning calorimetry and thermogravimetric analysis. Significant blue shift from the bulk absorption edge is observed in optical absorption as well as photoacoustic spectra indicating strong quantum confinement. The exciton transitions are better resolved in photoacoustic spectroscopy compared to optical absorption spectroscopy. We assign the first four bands observed in photoacoustic spectroscopy to 1se–1sh, 1pe–1ph, 1de–1dhand 2pe–2phtransitions using a non interacting particle model. Nonlinear absorption studies are done using z-scan technique with nanosecond pulses in the off resonant regime. The origin of optical limiting is predominantly two photon absorption mechanism.
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