Effect of molecular structure on the photochemical stability of acceptor and donor polymers used in organic solar cells

The limited operational lifetime of organic solar cells remains an obstacle to their commercial development and is largely due to the poor intrinsic photostability of the conjugated molecules that constitute the photoactive layer. Here, we selected a series of state-of-the-art donor and acceptor materials including PBDB-T, Y5, PF5-Y5, and PYT to study their photostability under AM1.5 simulated sunlight in ambient conditions. Their properties are monitored over time, using various spectroscopy techniques, including UV-Vis absorption, Fourier-transform infrared (FTIR), and X-ray and ultraviolet photoelectron spectroscopy (XPS and UPS). We found that the absorption spectra of Y5 and PYT films remain almost intact even after 30 hours of light exposure in air, while the PF5-Y5 and PBDB-T films undergo rapid photobleaching. The absorption losses observed in blend films of PBDB-T with Y5 and with PF5-Y5 can be understood as composed of contributions from the separate blend components that are similar to the absorption losses in neat films. The new peaks emerging in the FTIR spectra of PBDB-T, PF5-Y5, and their blend films witness the formation of new carbonyl groups, while these are absent in the spectra of the Y5 and PYT films. The XPS C 1s spectra of the PF5-Y5 and PBDB-T films confirm this carbonyl formation and the S 2p spectra reveal that sulphone groups are formed after 30 hours of exposure of these films. These results confirm that films of Y5 and the copolymer PYT are significantly more resistant to photooxidation, compared to the copolymer PF5-Y5. The comparison of these results suggests that the benzo[1,2-b:4,5-b ']dithiophene moiety with alkylated thiophenes as side chains (BDT-T) accelerates the photodegradation of PBDB-T and PF5-Y5. The replacement of the BDT-T unit by thiophene contributes to the enhanced stability of PYT, demonstrating that the nature of the co-monomer has a significant effect on the intrinsic photostability of Y5-based copolymers. These new insights are expected to stimulate the design of stable donors and acceptor polymers for the development of long-lived OPV devices. Absorption spectra show the photobleaching of acceptor copolymer PF5-Y5. The replacement of BDT-T by thiophene strongly improves the photostability.