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In this work, we have successfully introduced 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) as an efficient p-type dopant for donor–acceptor (D–A) co-polymer poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b;3,4-b′]dithiophene)-alt-4,7(2,1,3-benzothiadiazole)] (PCPDTBT) as an HTM in mesoscopic perovskite solar cells (PSCs). The bulk conductivity is significantly enhanced by 4 orders of magnitude when PCPDTBT is doped with F4TCNQ (6%, w/w). UV-vis and Fourier transform infrared spectroscopy (FTIR) results indicate the occurrence of p-doping, which results in higher bulk conductivity. The high conductivity leads to an impressive overall efficiency of 15.1%, which is considerably higher than the pristine PCPDTBT based devices (9.2%). The superior performance obtained should be largely attributed to the significant enhancement of the photocurrent density strongly correlated with a more efficient charge collection. This is the highest efficiency reported so far for PCPDTBT-based PSCs. Thus, molecularly p-doping has been demonstrated to be an effective strategy for further improving the performance of a wide range of D–A and other types of polymeric HTMs in PSCs.

High-efficiency perovskite solar cells employing a conjugated donor–acceptor co-polymer as a hole-transporting material