Correlation between the fine structure of spin-coated PEDOT:PSS and the photovoltaic performance of organic/crystalline-silicon heterojunction solar cells

We investigated the relationship between the fine structure of spin-coated conductive polymer poly(3,4-ethylenedioxythiphene):poly(styrene sulfonate) (PEDOT:PSS) films and the photovoltaic performance of PEDOT:PSS crystalline-Si (PEDOT:PSS/c-Si) heterojunction solar cells. Real-time spectroscopic ellipsometry revealed that there were two different time constants for the formation of the PEDOT:PSS network. Upon removal of the polar solvent, the PEDOT:PSS film became optically anisotropic, indicating a conformational change in the PEDOT and PSS chain. Polarized Fourier transform infrared attenuated total reflection absorption spectroscopy and Raman spectroscopy measurements also indicated that thermal annealing promoted an in-plane π-conjugated Cα = Cβ configuration attributed to a thiophene ring in PEDOT and an out-of-plane configuration of -SO3 groups in the PSS chain with increasing composition ratio of oxidized (benzoid) to neutral (quinoid) PEDOT, Iqui/Iben. The highest power conversion efficiency for the spin-coated PEDOT:PSS/c-Si heterojunction solar cells was 13.3% for Iqui/Iben = 9–10 without employing any light harvesting methods.