Polymorphs of the n‐Type Polymer P(NDI2OD‐T2): A Comprehensive Description of the Impact of Processing on Crystalline Morphology and Charge Transport

Abstract A systematic study of the polymorphs emerging in P(NDI2OD‐T2) (also commercially known as N2200), a prototypical organic semiconducting n‐type polymer, is presented. Using a tightly integrated experimental and computational approach, detailed atomistic‐level descriptions are provided investigating the three known P(NDI2OD‐T2) polymorphs observed at room temperature as a function of thin‐film processing. Importantly, over the course of the work, a missing link is uncovered, a fourth polymorph referred to here as Form I‐𝜷; this new form is a morphological intermediary observed upon thermal annealing, which evolves from Form I but tends to disappear upon full polymer chain melting. The computationally derived polymorph structures show excellent agreement with experimental X‐ray scattering characterization. The relative stabilities of each polymorph are calculated in terms of both the bulk material and the polymorph‐air interface. An energy landscape is then constructed to qualitatively compare the thermodynamic versus kinetic origins of each polymorph, and the factors driving (supra)assembly and associated transformations among polymorphs using an approach generalizable to other organic semiconducting polymers. Lastly, the relationships among preferential polymorphic crystallinity, relative chain orientations, and directional charge transport properties in P(NDI2OD‐T2) are explored. Overall, this work provides unprecedented insights into complex structure‐processing‐transport relationships in a representative semiconducting organic polymer.