Praveen Thoniyot

Nanoparticle Cluster Arrays for High-Performance SERS through Directed Self-Assembly on Flat Substrates and on Optical Fibers

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.

Inherently reproducible fabrication of plasmonic nanoparticle arrays for SERS by combining nanoimprint and copolymer lithography.

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.

Engineering 3D Nanoplasmonic Assemblies for High Performance Spectroscopic Sensing.

We demonstrate the fabrication of plasmonic sensors that comprise gold nanopillar arrays exhibiting high surface areas, and narrow gaps, through self-assembly of amphiphilic diblock copolymer micelles on silicon substrates. Silicon nanopillars with high integrity over arbitrary large areas are obtained using copolymer micelles as lithographic templates. The gaps between metal features are controlled by varying the thickness of the evaporated gold. The resulting gold metal nanopillar arrays exhibit an engineered surface topography, together with uniform and controlled separations down to sub-10 nm suitable for highly sensitive detection of molecular analytes by Surface Enhanced Raman Spectroscopy (SERS). The significance of the approach is demonstrated through the control exercised at each step, including template preparation and pattern-transfer steps. The approach is a promising means to address trade-offs between resolutions, throughput, and performance in the fabrication of nanoplasmonic assemblies for sensing applications.

Fluctuation in surface enhanced Raman scattering intensity due to plasmon related heating effect

Temporal changes in signal intensity of Surface Enhanced Raman Scattering (SERS) upon laser excitation is an interesting phenomenon in plasmonics. In-depth understanding of the phenomena is highly important especially when developing a SERS sensor based on the intensity variation of particular Raman peak/band. One of the main challenges in such a technique is the intensity reduction at a given location upon consecutive measurements. Previously, signal loss in SERS measurement was attributed to the electric-field induced roughness relaxations in the SERS active surface. In such cases, as the surface is smoothened out, signals are completely lost. In our observation, the reduction in the spectral intensity is irreversible but never completely lost and a major part of it can be attributed to the plasmon induced heating effect. Here, we experimentally demonstrate this effect by studying the SERS signal from four different Raman active molecules adsorbed onto substrates that contain uniform nano-roughened bi-metallic silver/gold coating. Possible mechanism that leads to irreversible signal loss is explained. Moreover, solutions for minimising such plasmonic heating when developing a biosensor are also discussed.