Positive to negative photoconductance switching in plasmonic gold nanoparticle networks

The elaboration of versatile materials in which electrical conduction is tuned by light irradiation is of paramount relevance to such diverse applications as photodetectors, photodiodes, solar cells or light sensors. Although positive photoconductance is increasingly common, systems with negative photoconductance are scarcely reported. In this work, a switching from positive to negative photoconductance is observed upon simple annealing of well-organized networks of gold nanoparticles stabilized by dodecanethiols. The photoconductance properties are investigated experimentally using impedance spectroscopy. The measured Nyquist plots and resonance curves of the impedance are analyzed in terms of equivalent electrical circuits consisting in parallel resistance, capacitance and photoconductance. The positive and negative photo-current conversion efficiencies of the nanoparticles network are estimated k P P C = 389 ± 40 n S . W − 1 . c m 2 and k N P C = − 241 ± 40 n S . W − 1 . c m 2 , respectively. With the aid of density functional theory calculations, the origin of the photoconductance is discussed, at the nanoscale level, in terms of changes of molecular conformation. Such molecular effects assist charge carrier tunneling between first neighbor nanoparticles, and favor the formation of traps introduced by the annealing of the sample. The present work contributes to the understanding of plasmo-electronic properties of hybrid molecule-nanoparticle self-assembled nano-structures.