Manipulating Conjugated Polymer Backbone Dynamics through Controlled Thermal Cleavage of Alkyl Side Chains. Issue 24 (18th August 2022) - Zhao, Haoyu
Abstract: The morphological stability of an organic photovoltaic (OPV) device is greatly affected by the dynamics of donors and acceptors occurring near the device's operational temperature. These dynamics can be quantified by the glass transition temperature ( T g ) of conjugated polymers (CPs). Because flexible side chains possess much faster dynamics, the cleavage of the alkyl side chains will reduce chain dynamics, leading to a higher T g . In this work, the T g s for CPs are systematically studied with controlled side chain cleavage. Isothermal annealing of polythiophenes featuring thermally cleavable side chains at 140 °C, is found to remove more than 95% of alkyl side chains in 24 h, and raise the backbone T g from 23 to 75 °C. Coarse grain molecular dynamics simulations are used to understand the T g dependence on side chain cleavage. X‐ray scattering indicates that the relative degree of crystallization remains constantduring isothermal annealing process. The effective conjugation length is not influenced by thermal cleavage; however, the density of chromophore is doubled after the complete removal of alkyl side chains. The combined effect of enhancing T g and conserving crystalline structures during the thermal cleavage process can provide a pathway to improving the stability of optoelectronic properties in future OPV devices. Abstract : Isothermal annealing is found to control the glass transition temperature ( T g ) of thermocleavable conjugated polymers. The backbone T g is enhanced with the removal of alkyl side chains while the crystalline domains remain the same during the process. After 24 h at 140 °C annealing, the original P3ET converts to PT‐COOH after alkyl side chains cleavage, where T g is increased from 23 to 75 °C.