Auke J. Kronemeijer

A selenophene-based low-bandgap donor-acceptor polymer leading to fast ambipolar logic.

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.

Molecular origin of high field-effect mobility in an indacenodithiophene–benzothiadiazole copolymer

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(-1) s(-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 π-stacking bridges.

A new thiophene substituted isoindigo based copolymer for high performance ambipolar transistors

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).

Photovoltaic and field effect transistor performance of selenophene and thiophene diketopyrrolopyrrole co-polymers with dithienothiophene

Here we report the synthesis of two new alternating co-polymers of thiophene and selenophene flanked diketopyrrolopyrrole with dithienothiophene. We find that the inclusion of the rigid fused dithienothiophene co-monomer affords semi-crystalline polymers, that exhibit promising ambipolar field effect transistor performance, with hole mobilities up to 0.23 cm2 V−1 s−1. The selenophene containing co-polymer exhibits a reduced band gap compared to the thiophene co-polymer, as a result of stabilisation of the polymer LUMO and destabilisation of the HOMO. The thiophene co-polymer exhibits promising solar cell performance in blends with PC71BM, with device efficiencies up to 5.1%.

Upscaling, integration and electrical characterization of molecular junctions

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.

Polaron hopping mediated by nuclear tunnelling in semiconducting polymers at high carrier density

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.

Two-Dimensional Carrier Distribution in Top-Gate Polymer Field-Effect Transistors: Correlation between Width of Density of Localized States and Urbach Energy

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.

Space-charge-limited hole current in poly(9,9-dioctylfluorene) diodes

Characterization of the hole transport in blue-emitting polymers as poly(9,9-dioctylfluorene) (PFO) is strongly hindered by their large ionization potential of ∼6 eV. Using common anodes as poly(3,4-ethylenedioxythiophene)/poly(styrenesulphonic acid) leads to a strongly injection limited current. We demonstrate that molybdenum trioxide forms an Ohmic hole contact on PFO, enabling the observation of a space-charge-limited current(SCLC). This allows a direct determination of the hole mobility PFO of 1.3×10−9 m2/V s at room temperature, in good agreement with previously reported mobility values determined by time-of-flight measurements.

Impact of derivatization on electron transmission through dithienylethene-based photoswitches in molecular junctions

We report a combined Non-Equilibrium Greens Function - Density Functional Theory study of molecular junctions made of photochromic diarylethenes between gold electrodes. The impact of derivatization of the molecule on the transmission spectrum is assessed by introducing: (i) substituents on the diarylethene core; and (ii) linker substituents between the gold surface and the diarylethene. We illustrate that substituents on the core shift considerably the HOMO/LUMO level energies in gas phase but do not change the I-V characteristics of the molecular junctions; this behaviour has been rationalized by establishing links between the transmission spectrum and interfacial electronic reorganization upon chemisorption. In contrast, the different linker substituents under study modulate the conductivity of the junction by changing the degree of orbital hybridization with the metallic electrodes and the degree of orbital polarization.

Electrical characteristics of conjugated self-assembled monolayers in large-area molecular junctions

We have studied the electrical characteristics of close-packed monolayers of conjugated para-phenylene oligomers as a function of molecular length in large-area molecular junctions. An exponential increase in resistance with molecular length is observed, Rexp (βL), with β=0.26±0.04 A-1 and β=0.20±0.06 A-1 for dithiol and monothiol derivatives, respectively. The decay coefficients are lower than previously determined experimentally using scanning probe or breakjunction techniques. We tentatively explain the low values by the forced planer geometry of the self-assembled molecules.