Ultra-high resolution imaging of thin films and single strands of polythiophene using atomic force microscopy.

Real-space images of polymers with sub-molecular resolution could provide valuable insights into the relationship between morphology and functionality of polymer optoelectronic devices, but their acquisition is problematic due to perceived limitations in atomic force microscopy (AFM). We show that individual thiophene units and the lattice of semicrystalline spin-coated films of polythiophenes (PTs) may be resolved using AFM under ambient conditions through the low-amplitude (≤ 1 nm) excitation of higher eigenmodes of a cantilever. PT strands are adsorbed on hexagonal boron nitride near-parallel to the surface in islands with lateral dimensions ~10 nm. On the surface of a spin-coated PT thin film, in which the thiophene groups are perpendicular to the interface, we resolve terminal CH3-groups in a square arrangement with a lattice constant 0.55 nm from which we can identify abrupt boundaries and also regions with more slowly varying disorder, which allow comparison with proposed models of PT domains.

Ground and Excited States of Bis-4-Methoxybenzyl-Substituted Diketopyrrolopyrroles: Spectroscopic and Electrochemical Studies.

A series of symmetrically bis-4-methoxybenzyl (4MB) N-substituted 1,4-diketopyrrolo[3,4-c]pyrrole (DPP) derivatives have been synthesized. The 4MB unit makes the DPP core soluble, and shows subtle modification of up to 0.2 eV in ground and excited states of the core when compared with related alkyl derivatives. Absorption and emission spectroscopy, as well as electrochemical and computational methods have been employed to prove the importance of the peripheral aryl units on the donor/ acceptor properties of the molecules. The 4MB products are highly fluorescent (quantum yields approaching 100 % in solution), with a unique distribution of frontier states shown by spectroelectrochemistry. The solid-state fluorescence correlates with the X-ray crystal structures of the compounds, a Stokes shift of approximately 80 nm is seen for two of the compounds. The frontier energy levels show that this subtle substitutional change could be of future use in molecular energy level tailoring in these, and related, materials for organic (opto)electronics.