Correlation and Characterization of Three-Dimensional Morphologically Dependent Localized Surface Plasmon Resonance Spectra of Single Silver Nanoparticles Using Dark-Field Optical Microscopy and Spectroscopy and Atomic Force Microscopy

Abstract

We have developed a new and effective methodology to correlate optical and AFM images of single Ag nanoparticles (NPs), allowing us to study 3D-morphological dependent localized surface plasmon resonance (LSPR) spectra of individual Ag NPs. We fabricated arrays of distinctive microwindows on glass coverslips using photo-lithography method, and created well-isolated individual Ag NPs with a wide variety of shapes and morphologies on the glass coverslips using a modified nanosphere lithography method (NSL). Using distinctive geometries of microwindows, we located individual Ag NPs of interest in their optical and AFM images, enabling us to correlate and characterize the LSPR spectra and 3D morphologies of the same single NPs using dark-field optical microscopy and spectroscopy (DFOMS) and AFM, respectively. We found that LSPR spectra of single Ag NPs, with nearly equal volume [(8.6 ± 0.4) × 10(3) nm(3)], cross-section [(2.2 ± 0.2) × 10(2) nm(3)], and height (39.6 ± 3.6 nm), highly depend on their shapes, showing the red shift of peak wavelength to 629 nm (quasi trapezoidal cylindrical NP) from that of 506 nm (quasi circular cylindrical NP). LSPR spectra of single Ag NPs simulated using discrete dipole approximation (DDA) agree well with those measured experimentally when their shapes and morphologies can be accuractely described in both methods, but differ when they are not. Furthermore, we found location-dependent LSPR spectra on and around a single NP, offering a unique opportunity to characterize multi-mode plasmonic NPs at nanometer resolution for better understanding their plasmonic optical properties and for rational design of single NP optics.