Liquid crystalline self-assembly of azulene-thiophene hybrids and their applications as OFET materials.

Orientational control within thin films is crucial for the preparation of organic field effect transistors (OFETs). The highly ordered liquid crystalline smectic E phase (SmE) is known as a powerful template for solution processed thin films. Here, we describe the synthesis and characterization of three novel azulene-thiophene hybrid materials. Liquid crystalline characterization showed the presence of wide SmE phases. Thin films were prepared by spin-coating at mesophase temperature. Due to the self-aligning properties of the SmE phase uniformly flat films with good molecular alignment were manufactured. Top contact bottom gate OFETs showed mobilities up to (3.3 ± 0.5) × 10-3 cm2 V-1 s-1.

Fabrication of planarly-oriented polycrystalline thin films of smectic liquid crystalline organic semiconductors.

Fabrication of planarly-oriented polycrystalline thin films of organic semiconductors was investigated, in which molecules sit parallel, i.e., "face-on" on the substrate so as to allow vertical charge transport favorably through a thin film. With the aid of self-organization of liquid crystalline molecules and an over-coated orientation layer, tens of nm thin films vertically oriented can be re-oriented from "hemeotropic, or vertical" to "homogenous or planar" to achieve polycrystalline thin films planarly oriented after removing the over-coated orientation layer. We investigated the key factors to affect re-orientation of the films and uniformity and surface morphology of the resulting films, including conditions required for the re-orientation and properties of the orientation layer materials and liquid crystals.

Universally Exhaustive Generation of Molecular Structures and Prediction of Their Electronic States Using Machine Learning for N-type Organic Transistor Materials.

We have proposed a new method for the exploration of organic functional molecules, using an exhaustive molecular generator combined without combinatorial explosion and electronic state predicted by machine learning and adapted for developing n-type organic semiconductor molecules for field-effect transistors. Our method first enumerates skeletal structures as much as possible and next generates fused ring structures using substitution operations for atomic nodes and bond edges. We have succeeded in generating more than 4.8 million molecules. We calculated the electron affinity (EA) of about 51 thousand molecules with DFT calculation and trained the graph neural networks to estimate EA values of generated molecules. Finally, we obtained the 727 thousand molecules as candidates that satisfy EA values over 3 eV. The number of these possible candidate molecules is far beyond what we have been able to propose based on our knowledge and experience in synthetic chemistry, indicating a wide diversity of organic molecules.

Scalable Ultrahigh-Speed Fabrication of Uniform Polycrystalline Thin Films for Organic Transistors.

The fabrication of organic semiconductor thin films by printing technologies is expected to enable the low-cost production of devices such as flexible display drivers, RF-ID tags, and various chemical/biological sensors. However, large-scale high-speed fabrication of uniform semiconductor thin films with adequate electrical properties for these devices remains a big challenge. Herein, we demonstrate an ultrafast and scalable fabrication of uniform polycrystalline thin films with 100% surface coverage using liquid crystalline semiconductors such as 2-phenyl-7-decyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) and 2.7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT-C8), at a rate of 3 orders of magnitude higher than before, i.e., 40 mm/s (2.4 m/min) or more by dip-coating in the drainage regime. Organic transistors fabricated with polycrystalline thin films of Ph-BTBT-10 show average mobilities of 4.13 ± 0.75 cm2/(V s) in the bottom-gate-bottom-contact configuration and 10.90 ± 2.40 cm2/(V s) in the bottom-gate-top-contact configuration comparable to those of the devices prepared with single-crystalline thin films. More importantly, these films almost maintain the FET performance when the substrate size is extended up to 4 square inch. The present findings are available for other liquid crystalline semiconductors and bring us one step closer to the realization of printed electronics.

Ambipolar transport in the smectic E phase of 2-propyl-5''-hexynylterthiophene derivative over a wide temperature range.

5-Hexyl-5''-hexynyl-2,2':5',2''-terthiophene exhibits the smectic E phase below 200 degrees C and does not crystallize when it is cooled to -100 degrees C. Between 200 and -100 degrees C, non-dispersive transport is observed for holes and electrons with time-of-flight spectroscopy. Over the entire temperature range, the electron mobility is approximately twice as high as that of the hole. The hole and electron transport characteristics in the smectic phase below 0 degrees C are explained by the Gaussian disorder model, which was proposed for amorphous organic semiconductors. The disorder parameters, sigma and Sigma, are almost the same for holes and electrons. However, the pre-exponential parameter mu(0) for the electron is twice as large as that for the hole, which can be attributed to the difference in the extension of the LUMO of the molecules. The energetic disorder sigma is primarily determined by the disorder in the orientation of the permanent dipoles of liquid crystal molecules.

Reinvestigation of carrier transport properties in liquid crystalline 2-phenylbenzothiazole derivatives.

We have reinvestigated the charge carrier transport properties in a liquid crystal of 2-(4'-heptyloxyphenyl)-6-dodecylthiobenzothiazole (7O-PBT-S12), for which the electronic conduction was first established in rodlike liquid crystals and for which the highest hole mobility in the smectic A (SmA) phase ever achieved was reported. We found that 7O-PBT-S12 exhibited three crystal phases, one of which appeared in a limited temperature range of 10 degrees just below the phase transition temperature from the SmA phase. In this crystal phase, nondispersive transient photohole currents were observed in time-of-flight experiments, and its hole mobility was determined to be 8 x 10(-3) cm(2)/Vs, slightly higher than that reported previously in the SmA phase. For the SmA phase, however, the hole mobility was 1 x 10(-4) cm(2)/Vs. Furthermore, we established the electron transport in the SmA phase of purified 7O-PBT-S12, whose mobility was the same as the hole mobility in that phase. In order to confirm generality of the new findings in 7O-PBT-S12, we investigated the carrier transport properties of its derivative having a short hydrocarbon chain, 2-(4'-heptyloxyphenyl)-6-butylthiobenzothiazole (7O-PBT-S4), and obtained comparable results. The present results correct a mistake in the previous report and give an idea of what a typical mobility in the SmA phase is. On the basis of these results, we discuss what determines the charge carrier mobility in smectic mesophases.

Electronic and ionic transports for negative charge carriers in smectic liquid crystalline photoconductor.

We have investigated negative charge carrier transport in the smectic mesophases of the 2-phenylnaphthalene derivative, 6-(4'-octylphenyl)-2-dodecyloxynaphthalene (8-PNP-O12), using the time-of-flight (TOF) method. We revealed that the negative charge carrier transport in its smectic mesophases had two different mechanisms, i.e., electronic and ionic conductions: we observed two transits of the carriers in both the smectic A (SmA) and smectic B (SmB) phases and demonstrated their origins by dilution experiments with a hydrocarbon (n-dodecane); the fast transit was attributed to the electronic transport of electrons and the slow one to the ionic transport of negative ions. Furthermore, it was clarified that the ionic transport was caused by small amounts of chemical impurities ionized by trapping photogenerated electrons in 8-PNP-O12 in addition to photoinduced autoionization of the impurities. Furthermore, we determined the trapping lifetimes for electrons to be 140 and 24 mus for the SmA and SmB phases, respectively. The experimental results suggest the coexistence of two distinctive transport channels for these charge carriers in the smectic mesophases.

Charge carrier transport properties in polymer liquid crystals containing oxadiazole and amine moieties in the same side chain.

Steady-state and transient photocurrent measurements were carried out to study the charge carrier transport properties of polymer liquid crystal (LC) containing oxadiazole (OXD) and amine moieties in the same side chain. The steady-state photocurrent measurement with asymmetric electrodes of ITO and Al and a short penetration depth of the illumination light indicated that both electrons and holes can be transported in this film. The transient hole photocurrent observed by time-of-flight (TOF) experiments was dispersive at room temperature. The hole drift mobility significantly depended on temperature and electric field and was determined to be 6.1 x 10(-8) cm2/Vs at a field of 9.1 x 10(5) V/cm. According to the disorder formalism, the Gaussian width of the density of states was determined to be 170 meV for holes. Despite the indication of possible electron transport in this film, we could not determine the electron mobility by TOF experiments due to strong dispersive photocurrent. We discuss the present charge transport properties of the film in relation to a large dipole attributed to an electrical push-pull structure of p-dimethylaminophenyl-substitited OXD moiety in polymer LC and its electroluminescent properties.

Liquid crystals for organic thin-film transistors.

Crystalline thin films of organic semiconductors are a good candidate for field effect transistor (FET) materials in printed electronics. However, there are currently two main problems, which are associated with inhomogeneity and poor thermal durability of these films. Here we report that liquid crystalline materials exhibiting a highly ordered liquid crystal phase of smectic E (SmE) can solve both these problems. We design a SmE liquid crystalline material, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), for FETs and synthesize it. This material provides uniform and molecularly flat polycrystalline thin films reproducibly when SmE precursor thin films are crystallized, and also exhibits high durability of films up to 200 °C. In addition, the mobility of FETs is dramatically enhanced by about one order of magnitude (over 10 cm(2) V(-1) s(-1)) after thermal annealing at 120 °C in bottom-gate-bottom-contact FETs. We anticipate the use of SmE liquid crystals in solution-processed FETs may help overcome upcoming difficulties with novel technologies for printed electronics.

Hole mobility and lifetime in a smectic liquid crystalline photoconductor of a 2-phenylnaphthalene derivative.

We have investigated hole transport properties in the smectic mesophases of a 2-phenylnaphthalene derivative 6-(4'-octylphenyl)-2-dodecyloxynaphthalene in detail by using time-of-flight technique. The transient photocurrents were measured in liquid-crystal cells with various thickness from 5 to 700 microm. They were well defined and nondispersive in the smectic A (SmA) phase up to 500 microm and in the smectic B (SmB) phase within the entire thickness employed, while they exhibited an exponential decay in the SmA phase at 700 microm. The mobilities in the SmA and SmB phases were constant in each mesophase irrespective of the cell thickness, and were 2.5 x 10(-4) and 1.7 x 10(-3) cm2V s, respectively. The hole lifetimes were determined to be 10 ms and longer than 5 ms for the SmA and SmB phases, respectively. We discuss the origin of these lifetimes from the two points of view, i.e., hole trapping by a trace amount of existing impurities and recombination with negative ionic charges. We conclude that impurities are mainly responsible for the present hole lifetime test.