Electrochemical growth of three-dimensionally ordered macroporous metals as photonic crystals

Abstract

Over the last two decades three dimensionally ordered macroporous (3-DOM) materials have turned out to be very promising in many applications ranging from optics, plasmonics, to catalyst scaffolds. The thesis presents a systematic study on formation and characterisation of 3-DOM metals as photonic crystals. Metals are nearly perfect reflectors with low adsorption at microwave or millimetre wavelengths. Meanwhile they generally absorb visible light because of their negative imaginary part of the dielectric constant that could destroy the band gap in the visible though they. Howevers, for noble metals such as gold, silver and copper, considering the Drude-like behaviour, the adsorption will be small enough to achieve a complete photonic band gap for optical or even shorter wavelengths, with silver performing the best. In order to fabricate the 3-DOM metallic nanostructures, template-directed electrochemical deposition has been employed in which, initially a highly ordered film of submircon sized colloidal spheres is deposited on to electronically conducting substrates, for instance, indium-tin oxide (ITO) coated glass substrate, through evaporation-induced self-assembly; and subsequently it is infiltrated with metallic elements electrochemically reduced from corresponding electrolytes; fiannly removal of the colloidal templating film reveals a metallic film comprised of periodically arranged spherical voids. Field Emission Gun Scanning Electron Microscopy (FEGSEM) was used to examine the surface morphology and periodicity of the 3-DOM metallic films. It revealed that highly ordered structures are homogenous and uniform over a large scale for both the original colloidal templates and metallic inverse structures. However for silver electroplated from either silver thiosulfate or silver chlorate bath, voids in the template are fully infiltrated, including both the interstitial spaces between the colloidal spheres and any cracks between film domains, forming a complete solid network over large length scales; for copper the filling factors are strongly dependent on the bath chemistry and in copper sulfate bath isolated macroporous domains can be formed due to those in the cracks will be dissolved back to the solution while those reduced from copper glycerol bath resulted in fully infiltrated structures. Moreover, angle-resolved reflectance spectroscopy has further confirmed the three-dimensional periodicity and indicated the inverse structures have stop band properties in the visible wavelength region, consistent with variation in the effective refractive index of the films. In addition, surface enhanced Raman scattering (SERS) spectroscopy has been used to evaluate applications of the inverse metals as SERS-active substrates. SERS has nearly exclusively been associated with three noble metals copper, silver (by far the most important) and gold. The 3-DOM metallic thin films possess excellent features for SERS detection arising from their long range periodical void geometry, which gives significant enhancement to Raman intensity. Preliminary measurements have demonstrated the 3-DOM metallic structures are well suited for SERS enhancement. Series spectra from different points of each specimen have given reproducible intensities. Variables associated with Raman intensity such as pore size, dye concentration, and film thickness, have been tuned to achieve maximal enhancement for visible and near-IR wavelengths.