摘要： Solar cells constructed with well-ordered polythiophene (PT) or other p-conjugated polymer ?lms are known to yield better photovoltaic characteristics. We recently constructed a PT-based solar cell (PTSC) wherein the photoactive PT ?lm was grown photoelectrochemically along a dye anchor, 3-{5-[N,N-bis(4-diphenylamino)phenyl]thieno[3,2-b]thiophen-2-yl}-2-cyano-acrylic acid (C207) pre-adsorbed onto a compact TiO2 layer. In an effort to understand the effects of other important factors contributing to the PTSC performance, we compared ex-situ and in-situ doping of ordered PT ?lms with three different alkylammonium cations, tetrabutylammonium (TBA+), tetraethylammonium (TEA+), and tetramethylammonium (TMA+). The PT ?lms that have undergone such ex- and in-situ doping both show higher open-circuit voltage (Voc) and short-circuit current density (Jsc) than their pristine counterparts. The optimal conversion ef?ciency (h) of 7.53 ± 0.58% was achieved via in-situ PT doping with TMA+. The incident photon-to-electron conversion ef?ciency (IPCE), electrochemical impedance, and electron lifetime measurements all indicate that in-situ doping is less affected by the cation size and can lead to a higher doping level than the ex-situ doping method. The IPCE also bene?ts from the use of a thin TiO2 layer, as more light reaches the PT ?lm to generate photohole/electron pairs. With the combined use of a thin layer of TiO2 and an ordered PT ?lm containing a large number of dopant ions, the photohole/electron recombination is signi?cantly suppressed.