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β-detected nuclear spin relaxation of (8)Li(+) has been used to probe the depth dependence of molecular dynamics in high- and low-molecular-weight deuterated polystyrene. The average nuclear spin-lattice relaxation rate, 1/T(avg)(1), is a measure of the spectral density of the polymer motion at the Larmor frequency (41 MHz at 6.55 T). In both samples, 1/T(avg)(1) is depth independent below ∼200 K but above this temperature it decreases approximately exponentially with distance from the free surface, returning to bulk behavior for depths greater than ∼10 nm. This is direct evidence for a region near the free surface with enhanced molecular dynamics compared with the bulk. The effective thickness of the surface region increases with increasing temperature and is finite even above the glass transition. These results present challenges for the current understanding of dynamics near the surface of polymer glasses.

Highly enhanced Raman scattering of graphene on a plasmonic nano-structure platform is demonstrated. The plasmonic platform consists of silver nano-structures in a periodic array on top of a gold mirror. The gold mirror is used to move the hot spot to the top surface of the silver nano-structures, where the graphene is located. Two different nano-structures, ring and crescent, are studied. The actual Raman intensity is enhanced by a factor of 890 for the G-peak of graphene on crescents as compared to graphene on a silicon dioxide surface. The highest enhancement is observed for the G-peak as compared to the 2D-peak. The results are quantitatively well-matched with a theoretical model using an overlap integral of incident electric field intensities with the corresponding intensities of Raman signals at the G- and 2D-peaks. The interaction of light with nano-structures is simulated using finite element method (FEM).

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