摘要： Conjugated polyelectrolytes are commonly employed as interlayers to modify organic solar cell (OSC) electrode work functions but their use as an electron donor in water-processed OSC active layers has barely been investigated. Here, we demonstrate that poly[3-(6’-N,N,N-trimethyl ammonium)-hexylthiophene] bromide (P3HTN) can be employed as an electron donor combined with a water-soluble fullerene (PEG-C60) into eco-friendly active layers deposited from aqueous solutions. Spin-coating a poly(3,4-ethylenedioxythiophene):polystyrene sulfonate (PEDOT:PSS) layer prior to the P3HTN:PEG-C60 active layer deposition considerably increases the open-circuit voltage (Voc) of the OSCs to values above 1.3 V. Along with this enhanced Voc, the OSCs fabricated with the PEDOT:PSS interlayers exhibit 10-fold and 5-fold increases in short-circuit current density (Jsc) with respect to those employing bare indium tin oxide (ITO) and molybdenum trioxide coated ITO anodes, respectively. These findings suggest that the enhanced Jsc and Voc in the water-processed OSCs using the PEDOT:PSS interlayer cannot be solely ascribed to a better hole collection but rather to ion exchanges taking place between PEDOT:PSS and P3HTN. We investigate the optoelectronic properties of the newly formed polyelectrolytes using absorption and photoelectron spectroscopy combined with hole transport measurements to elucidate the enhanced photovoltaic parameters obtained in the OSCs prepared with PEDOT:PSS and P3HTN.