| Summary: | The morphological, spectroscopic and rheological properties of silver nanoparticles (AgNPs) synthesized in situ within commercial PEDOT:PSS formulations, labeled PP@NPs, were systematically investigated by varying different synthetic parameters (NaBH<sub>4</sub>/AgNO<sub>3</sub> molar ratio, PEDOT:PSS formulation and silver and PEDOT:PSS concentration in the reaction medium), revealing that only the reagent ratio affected the properties of the resulting nanoparticles. Combining the results obtained from the field-emission scanning electron microscopy analysis and UV-Vis characterization, it could be assumed that PP@NPs’ stabilization occurs by means of PSS chains, preferably outside of the PEDOT:PSS domains with low silver content. Conversely, with high silver content, the particles also formed in PEDOT-rich domains with the consequent perturbation of the polaron absorption features of the conjugated polymer. Atomic force microscopy was used to characterize the films deposited on glass from the particle-containing PEDOT:PSS suspensions. The film with an optimized morphology, obtained from the suspension sample characterized by the lowest silver and NaBH<sub>4</sub> content, was used to fabricate a very initial prototype of a water-processable anode in a solar cell prepared with an active layer constituted by the benchmark blend poly(3-hexylthiophene) and [6,6]-Phenyl C61 butyric acid methyl ester (PC<sub>60</sub>BM) and a low-temperature, not-evaporated cathode (Field’s metal).
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