Reversible Thermochromic Nanocomposites Based on Thiolate-Capped Silver Nanoparticles Embedded in Amorphous Polystyrene

Abstract: Technologically useful reversible thermochromic materials can be prepared using very simple polymer-embedded nanostructures. In particular, silver nanoparticles capped by long-chain alkyl-thiolate molecules (i.e., Agx(SC_nH2_n+1)_y, with n > 10) spontaneously organize in aggregates because of the interdigitation phenomenon involving the linear alkyl chains bonded at surfaces of neighboring nanoparticles. Owing to the alkylchain interdigitation, nanoparticles very close to each other result and an interaction among their surface plasmon resonances may take place. Surface plasmon interaction causes a splitting of the absorption band whose characteristics depend on the aggregate shape. Since shape-less aggregates are generated, a multiple-splitting of the silver surface plasmon absorption band is observed, which causes a broad absorption spreading on the whole visible spectral region. Amorphous polystyrene containing interdigitated silver nanoparticles has a dark-brown or black coloration, depending on the nanoparticle numerical density, but since the inter-particle distance slightly increases at melting point of interdigitation crystallites a reversible termochromic effect is observed at this special temperature. In particular, the material coloration changes from dark-brown to yellow which is the coloration produced by the surface plasmon absorption of isolated silver nanoparticles. This reversible thermochromism can be finely controlled by modifying the structure of thiolate groups, and precisely, the strength of interactions acting inside the interdigitation crystallites.