Impact of the Nature of the Side‐Chains on the Polymer‐Fullerene Packing in the Mixed Regions of Bulk Heterojunction Solar Cells

Abstract

Polymer‐fullerene packing in mixed regions of a bulk heterojunction solar cell is expected to play a major role in exciton‐dissociation, charge‐separation, and charge‐recombination processes. Here, molecular dynamics simulations are combined with density functional theory calculations to examine the impact of nature and location of polymer side‐chains on the polymer‐fullerene packing in mixed regions. The focus is on poly‐benzo[1,2‐b:4,5‐b′]dithiophene‐thieno[3,4‐c]pyrrole‐4,6‐dione (PBDTTPD) as electron‐donating material and [6,6]‐phenyl‐C61‐butyric acid methyl ester (PC61BM) as electron‐accepting material. Three polymer side‐chain patterns are considered: i) linear side‐chains on both benzodithiophene (BDT) and thienopyrroledione (TPD) moieties; ii) two linear side‐chains on BDT and a branched side‐chain on TPD; and iii) two branched side‐chains on BDT and a linear side‐chain on TPD. Increasing the number of branched side‐chains is found to decrease the polymer packing density and thereby to enhance PBDTTPD–PC61 BM mixing. The nature and location of side‐chains are found to play a determining role in the probability of finding PC61BM molecules close to either BDT or TPD. The electronic couplings relevant for the exciton‐dissociation and charge‐recombination processes are also evaluated. Overall, the findings are consistent with the experimental evolution of the PBDTTPD–PC61BM solar‐cell performance as a function of side‐chain patterns.