Conjugated polymers enable the production of flexible semiconductor devices that can be processed from solution at low temperatures. Over the past 25 years, device performance has improved greatly as a wide variety of molecular structures have been studied. However, one major limitation has not been overcome; transport properties in polymer films are still limited by pervasive conformational and energetic disorder. This not only limits the rational design of materials with higher performance, but also prevents the study of physical phenomena associated with an extended π-electron delocalization along the polymer backbone. Here we report a comparative transport study of several high-mobility conjugated polymers by field-effect-modulated Seebeck, transistor and sub-bandgap optical absorption measurements. We show that in several of these polymers, most notably in a recently reported, indacenodithiophene-based donor-acceptor copolymer with a near-amorphous microstructure, the charge transport properties approach intrinsic disorder-free limits at which all molecular sites are thermally accessible. Molecular dynamics simulations identify the origin of this long sought-after regime as a planar, torsion-free backbone conformation that is surprisingly resilient to side-chain disorder. Our results provide molecular-design guidelines for 'disorder-free' conjugated polymers.

One of the most inspiring and puzzling developments in the organic electronics community in the last few years has been the emergence of solution-processable semiconducting polymers that lack significant long-range order but outperform the best, high-mobility, ordered semiconducting polymers to date. Here we provide new insights into the charge-transport mechanism in semiconducting polymers and offer new molecular design guidelines by examining a state-of-the-art indacenodithiophene-benzothiadiazole copolymer having field-effect mobility of up to 3.6 cm 2 V À 1 s À 1 with a combination of diffraction and polarizing spectroscopic techniques. Our results reveal that its conjugated planes exhibit a common, comprehensive orientation in both the non-crystalline regions and the ordered crystallites, which is likely to originate from its superior backbone rigidity. We argue that charge transport in high-mobility semiconducting polymers is quasi one-dimensional, that is, predominantly occurring along the backbone, and requires only occasional intermolecular hopping through short p-stacking bridges.

Fast ambipolar CMOS-like logic is demonstrated using a new selenophene-based donor-acceptor polymer semiconductor. The polymer exhibits saturation hole and electron mobilities of 0.46 cm(2) /Vs and 0.84 cm(2) /Vs. Inverters are fabricated with high gains while three-stage ring oscillators show stable oscillation with an unprecedented maximum frequency of 182 kHz at a relatively low supply voltage of 50 V.

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A novel thiophene substituted isoindigo and its copolymer with benzothiadiazole have been synthesized. The polymer with low lying LUMO energy levels exhibits excellent ambipolar behavior in field effect transistors with both hole and electron mobilities recorded over 0.1 cm(2) V(-1) s(-1).

A general semiconductor‐independent two‐dimensional character of the carrier distribution in top‐gate polymer field‐effect transistors is revealed by analysing temperature‐dependent transfer characteristics and the sub‐bandgap absorption tails of the polymer semiconductors. A correlation between the extracted width of the density of states and the Urbach energy is presented, corroborating the 2D accumulation layer and demonstrating an intricate connection between optical measurements concerning disorder and charge transport in transistors.

The ultimate target of molecular electronics is to combine different types of functional molecules into integrated circuits, preferably through an autonomous self-assembly process. Charge transport through self-assembled monolayers has been investigated previously, but problems remain with reliability, stability and yield, preventing further progress in the integration of discrete molecular junctions. Here we present a technology to simultaneously fabricate over 20,000 molecular junctions-each consisting of a gold bottom electrode, a self-assembled alkanethiol monolayer, a conducting polymer layer and a gold top electrode-on a single 150-mm wafer. Their integration is demonstrated in strings where up to 200 junctions are connected in series with a yield of unity. The statistical analysis on these molecular junctions, for which the processing parameters were varied and the influence on the junction resistance was measured, allows for the tentative interpretation that the perpendicular electrical transport through these monolayer junctions is factorized.

The transition rate for a single hop of a charge carrier in a semiconducting polymer is assumed to be thermally activated. As the temperature approaches absolute zero, the predicted conductivity becomes infinitesimal in contrast to the measured finite conductivity. Here we present a uniform description of charge transport in semiconducting polymers, including the existence of absolute-zero ground-state oscillations that allow nuclear tunnelling through classical barriers. The resulting expression for the macroscopic current shows a power-law dependence on both temperature and voltage. To suppress the omnipresent disorder, the predictions are experimentally verified in semiconducting polymers at high carrier density using chemically doped in-plane diodes and ferroelectric field-effect transistors. The renormalized current-voltage characteristics of various polymers and devices at all temperatures collapse on a single universal curve, thereby demonstrating the relevance of nuclear tunnelling for organic electronic devices.