Effects of the Donor Unit on the Formation of Hybrid Layers of Donor-Acceptor Copolymers with Silver Nanoparticles.

Donor-acceptor (D-A) copolymers containing perylene-3,4,9,10-tetracarboxydiimide (PDI) electron-acceptor (A) units belonging to n-type semiconductors are of interest due to their many potential applications in photonics, particularly for electron-transporting layers in all-polymeric or perovskite solar cells. Combining D-A copolymers and silver nanoparticles (Ag-NPs) can further improve material properties and device performances. Hybrid layers of D-A copolymers containing PDI units and different electron-donor (D) units (9-(2-ethylhexyl)carbazole or 9,9-dioctylfluorene) with Ag-NPs were prepared electrochemically during the reduction of pristine copolymer layers. The formation of hybrid layers with Ag-NP coverage was monitored by in-situ measurement of absorption spectra. The Ag-NP coverage of up to 41% was higher in hybrid layers made of copolymer with 9-(2-ethylhexyl)carbazole D units than in those made of copolymer with 9,9-dioctylfluorene D units. The pristine and hybrid copolymer layers were characterized by scanning electron microscopy and X-ray photoelectron spectroscopy, which proved the formation of hybrid layers with stable Ag-NPs in the metallic state with average diameters <70 nm. The influence of D units on Ag-NP diameters and coverage was revealed.