Frustules of Amphora sp. as a photonic crystal with photoluminescent CdS nanoparticles.

Abstract

Diatom frustules have species-specific patterns of pores, striae, pores, and nanopores, periodically arranged on its silica surface, as sets of cavities that modify the vacuum electromagnetic density of states. Therefore, frustules may be considered photonic crystals; the interaction with light-emitting sources inside the pores may potentially result in enhancement or inhibition of their spontaneous radiative emission rate and frequencies. In this work, we studied the photoluminescence of cadmium sulfide nanoparticles (CdS-NP) deposited inside frustule cavities that conveyed evidence of cavity-NP interaction. We synthesized CdS-NP, a semiconductor compound achieving quantum dots small enough to impose confinement effects to the electronic states. CdS-NP and their clusters were physiosorbed onto the surface, striae, and predominantly inside the pores of the cleansed frustules of Amphora sp. A broad peak with a maximum intensity at 437 nm (2.84 eV) was recorded after excitation with a 375 nm light source, showing a large blue shift and signal amplification of the CdS-NP photoluminescence when these were embedded inside the pores of the silica frustule. Using the Brus equation, we estimated a NP size of 4.1 ± 0.2 nm for the CdS-NP snuggly packed inside the smaller pores of the frustule, of 10 ± 0.7 nm in average diameter, The emission Purcell enhancement factor for an emitting atom in a cavity was calculated. The obtained Q factor (c. 5) was smaller than typical Q factors for designed semiconductor cavities of similar dimensions, an expected situation if it is assumed that the pores are open-ended cavities.