Shape and size dependence of radiative, non-radiative and photothermal properties of gold nanocrystals

TLDR

Nanoparticle research has expanded rapidly, driven by interest in how atomic behavior scales with size, and metallic nanoparticles—especially gold—are prized for their intense colors arising from surface plasmon absorption. The article aims to elucidate the physical origin of gold nanoparticle surface plasmon absorption, examining how size, shape, and environment influence the resonance to enable its use as an analytical probe. Using Mie and Maxwell‑Garnett theory, the study models plasmon absorption and tracks its ultrafast changes under laser excitation to probe electron‑electron and electron‑phonon interactions. Plasmon resonance markedly enhances Raman signals of adsorbed molecules and boosts fluorescence quantum yield in gold nanorods.

Abstract

Driven by the search for new materials with interesting and unique properties and also by the fundamental question of how atomic and molecular physical behaviour develops with increasing size, the field of nanoparticle research has grown immensely in the last two decades. Partially for these reasons, colloidal solutions of metallic (especially silver and gold) nanoparticles have long fascinated scientists because of their very intense colours. The intense red colour of colloidal gold nanoparticles is due to their surface plasmon absorption. This article describes the physical origin of the surface plasmon absorption in gold nanoparticles with emphasis on the Mie and also the Maxwell-Garnett theory and reviews the effects of particle size and shape on the resonance condition. A better understanding of the relationship between the optical absorption spectrum (in particular, the plasmon resonance) and such particle properties as its dimensions or surrounding environment can prove fruitful for the use of the plasmon absorption as an analytical tool. The plasmon resonance has also had a great impact on the Raman spectrum of surface-adsorbed molecules and a large enhancement of the fluorescence quantum yield of gold nanorods is observed. Furthermore, following the changes in the plasmon absorption induced by excitation (heating) with ultrashort laser pulses allows one to monitor the electron dynamics (electron-electron and electron-phonon interactions) in real time, which is important in understanding such fundamental questions regarding the thermal and electrical conductivity of these nanoparticles. Very intense heating with laser pulses leads to structural changes of the nanoparticles (nuclear rearrangements in the form of melting and fragmentation).