Charge transport in conjugated polymer semiconductors has traditionally been thought to be limited to a low-mobility regime by pronounced energetic disorder. Much progress has recently been made in advancing carrier mobilities in field-effect transistors through developing low-disorder conjugated polymers. However, in diodes these polymers have to date not shown much improved mobilities, presumably reflecting the fact that in diodes lower carrier concentrations are available to fill up residual tail states in the density of states. Here, we show that the bulk charge transport in low-disorder polymers is limited by water-induced trap states and that their concentration can be dramatically reduced through incorporating small molecular additives into the polymer film. Upon incorporation of the additives we achieve space-charge limited current characteristics that resemble molecular single crystals such as rubrene with high, trap-free SCLC mobilities up to 0.2 cm 2 /Vs and a width of the residual tail state distribution comparable to k B T .

Efficient conjugated polymer optoelectronic devices benefit from concomitantly high luminescence and high charge carrier mobility. This is difficult to achieve, as interchain interactions, which are needed to ensure efficient charge transport, tend also to reduce radiative recombination and lead to solid-state quenching effects. Many studies detail strategies for reducing these interactions to increase luminescence, or modifying chain packing motifs to improve percolation charge transport; however achieving these properties together has proved elusive. Here, we show that properly designed amorphous donor- alt -acceptor conjugated polymers can circumvent this problem; combining a tuneable energy gap, fast radiative recombination rates and luminescence quantum efficiencies >15% with high carrier mobilities exceeding 2.4 cm 2 /Vs. We use photoluminescence from exciton states pinned to close-crossing points to study the interplay between mobility and luminescence. These materials show promise towards realising advanced optoelectronic devices based on conjugated polymers, including electrically-driven polymer lasers.

The exploration of a wide range of molecular structures has led to the development of high-performance conjugated polymer semiconductors for flexible electronic applications including displays, sensors, and logic circuits. Nevertheless, many conjugated polymer field-effect transistors (OFETs) exhibit nonideal device characteristics and device instabilities rendering them unfit for industrial applications. These often do not originate in the material's intrinsic molecular structure, but rather in external trap states caused by chemical impurities or environmental species such as water. Here, a highly efficient mechanism is demonstrated for the removal of water-induced traps that are omnipresent in conjugated polymer devices even when processed in inert environments; the underlying mechanism is shown, by which small-molecular additives with water-binding nitrile groups or alternatively water-solvent azeotropes are capable of removing water-induced traps leading to a significant improvement in OFET performance. It is also shown how certain polymer structures containing strong hydrogen accepting groups will suffer from poor performances due to their high susceptibility to interact with water molecules; this allows the design guidelines for a next generation of stable, high-performing conjugated polymers to be set forth.

We investigate in detail the optical, electrochemical, structural and electrical properties of polythiophenes with increasing content of polar side chains.