Donor Conjugated Polymers with Polar Side Chain Groups: The Role of Dielectric Constant and Energetic Disorder on Photovoltaic Performance

To better understand the correlation of the dielectric properties with the photovoltaic response in conjugated polymer:fullerene bulk heterojunction materials, the concept of introducing minimal structural change is employed to increase the polymer dielectric constant via polar cyano groups added to the end of butyl or octyl side chains in the poly(dithienosilole‐thienopyrrolodione) system. Density functional theory calculations confirm that the polar groups do not affect the polymer electronic structure but can lead to an increase in overall dipole moment depending on the polymer chain conformation. Despite the increased dielectric constant (from 2.7 to 4.3 for cyano‐octyl side chains and from 2.7 to 3.2 for the cyano‐butyl analogues), the device characteristics employing the cyano‐containing polymers are inferior to those of the devices made with unfunctionalized alkyl chains. It is found that the hole mobilities for the cyano‐containing polymers are two orders of magnitude lower compared to those for the parent polymers and suggest this is due to an increase in energetic disorder caused by the strong local permanent dipoles associated with the cyano groups. The study highlights the complexity in the relationship between the dielectric constant of organic materials, the morphologies that are induced, and their photovoltaic performance. Introducing polar cyano groups to the end of dithienosilole‐thienopyrrolodione polymer side chains leads to an increase in polymer dielectric constant, without significantly affecting the optical gaps and energy levels. However, this structural modification results in inferior device parameters and ultimately lower power conversion efficiencies, because of the drastic decrease in hole mobilities which is caused by higher energetic disorders.