Advanced Functional Materials, Vol.20, No.12, 1954-1961, 2010
Induced SER-Activity in Nanostructured Ag-Silica-Au Supports via Long-Range Plasmon Coupling
A novel Ag-silica-Au hybrid device is developed that displays a long-range plasmon transfer of Ag to Au leading to enhanced Raman scattering of molecules largely separated from the optically excited Ag surface. A nanoscopically rough Ag surface is coated by a silica spacer of variable thickness from similar to 1 to 21 nm and a thin Au film of similar to 25 nm thickness. The outer Au surface is further functionalized by a self-assembled monolayer (SAM) for electrostatic binding of the heme protein cytochrome c (Cyt c) that serves as a Raman probe and model enzyme. High-quality surface-enhanced resonance Raman (SERR) spectra are obtained with 413 nm excitation, demonstrating that the enhancement results exclusively from excitation of Ag surface plasmons. The enhancement factor is estimated to be 2 x 10(4)- 8 x 10(3) for a separation of Cyt c from the Ag surface by 28-47 nm, corresponding to an attenuation of the enhancement by a factor of only 2-6 compared to Cyt c adsorbed directly on a SAM-coated Ag electrode. Upon immobilization of Cyt c on the functionalized Ag-silica-Au device, the native structure and redox properties are preserved as demonstrated by time- and potential-dependent SERR spectroscopy.