Charge Transport Anisotropy in Highly Oriented Thin Films of the Acceptor Polymer P(NDI2OD-T2)

The nanomorphology of the high mobility polymer poly{[N,N′‐bis(2‐octyldodecyl)‐1,4,5,8‐naphthalenedicarboximide‐2,6‐diyl]‐alt‐5,5′‐(2,2′‐bithiophene)} P(NDI2OD‐T2) in thin films is explored as a function of different annealing conditions and correlated to optical and electrical properties. While nanofibrils with face‐on orientation in form I are obtained directly after spin‐coating and annealing below the melt transition temperature, clear evidence of lamellar structures is found after melt‐annealing followed by slow cooling to room temperature. Interestingly these structural changes are accompanied by distinct changes in the absorption patterns. Electron diffraction measurements further show clear transitions towards predominant edge‐on oriented chains in form II upon melt‐annealing. Large‐scale alignment with dichroic ratios up to 10 and improved order is achieved by high temperature rubbing and subsequent post‐rubbing annealing. These highly oriented morphologies allow anisotropic in‐plane charge transport to be probed with top‐gate transistors parallel and perpendicular to the polymer chain direction. Mobilities up to 0.1 cm2 V‐1 s‐1 are observed parallel to the polymer chain, which is up to 10 times higher than those perpendicular to the polymer chain. Large‐scale alignment of a high mobility, n‐type donor–acceptor polymer is achieved by high temperature rubbing of thin films, while post‐rubbing thermal annealing protocols strongly dictate the texture. These highly ordered and oriented layers exhibit anisotropic charge transport with enhanced electron mobilities along the polymer backbone as compared to the perpendicular direction.