Probing the Relationship between Molecular Structures, Thermal Transitions, and Morphology in Polymer Semiconductors Using a Woven Glass-Mesh-Based DMTA Technique
Journal article, 2019

The glass transition temperature (T-g) of polymers is an important parameter that determines the kinetics of molecular organization of polymeric chains. Understanding the T-g of conjugated polymers is critical in achieving a thermally stable and optimum morphology in polymer:polymer or polymer:small molecule blends in organic electronics. In this study, we have used the woven glass-mesh-based method of dynamic mechanical thermal analysis (DMTA) to evaluate the T-g of polymer semiconductors, which is generally not easy to detect using conventional techniques such as differential scanning calorimetry (DSC). More importantly, we establish the relationship between the thermal transitions and the molecular structure of polymer semiconductors. For conjugated polymers with rigid conjugated backbones and large alkyl side chains, we report the presence of separate thermal transitions corresponding to the polymer backbone as well as transitions related to side chains, with the latter being the most prominent. By systematically comparing polymer side chains, molecular weight, and backbone structure, the origin of the T-g and a sub-T-g transitions have been successfully correlated to the polymer structures. The antiplastization effect of additives has also been used to further prove the origin of the different transitions. Thermal transitions of a range of high performing polymers applied in organic photovoltaics, including TQ1, PTNT, PTB7, PTB7-Th, and N2200, have been systematically studied in this work. According to the measurements, some of these polymers have a very small amorphous part, changing the way the morphology should be described for these materials. We infer that the main phase in these polymers consists of hairy aggregates, with a few pi-stacked rigid polymer chains forming the aggregates.

Author

Anirudh Sharma

University of Bordeaux

Flinders University

Xun Pan

Flinders University

Jonas M. Bjuggren

Flinders University

Desta Gedefaw

University of the South Pacific

Flinders University

Xiaofeng Xu

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Renee Kroon

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Ergang Wang

Chalmers, Chemistry and Chemical Engineering, Applied Chemistry

Jonathan A. Campbell

Flinders University

David A. Lewis

Flinders University

Mats R. Andersson

Flinders University

Chemistry of Materials

0897-4756 (ISSN) 1520-5002 (eISSN)

Vol. 31 17 6740-6749

Subject Categories

Polymer Chemistry

Physical Chemistry

Polymer Technologies

DOI

10.1021/acs.chemmater.9b01213

More information

Latest update

11/11/2019