Liquid Crystalline Organic Semiconductors Research Articles

High-speed blade-coating using liquid crystalline organic semiconductor Ph-BTBT-10

We have investigated the fabrication of crystalline thin films of a liquid crystalline organic semiconductor (2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene: Ph-BTBT-10) by high-speed blade-coating at 140 mm s−1. Uniform crystalline Ph-BTBT-10 films were fabricated at temperatures over 50 °C, which is the temperature of the liquid crystal phase, without inhomogeneous recrystallization, despite the high-speed blade-coating. Transistors fabricated using these films showed a high average carrier mobility of 4.8 cm2 Vs−1 for 26 devices, with a coefficient of variation of only 7.3%. We concluded that liquid crystalline organic semiconductors are useful materials for high-speed meniscus-guided-coating for practical use.

High-Performance Organic Field-Effect Transistors of Liquid Crystalline Organic Semiconductor by Laser Mapping Annealing.

Organic semiconductors (OSCs), especially small molecule semiconductors, have received increasing attention due to their good designability and variability. Phase transitions and interfacial properties have a decisive influence on device performance. Here, 2-Dodecyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-12) devices are treated with low-power laser annealing, which is able to avoid the influence of the dewetting effect on the hole mobility of organic semiconductor materials. Ultraviolet ozone treatment and self-assembled monolayer treatment can improve the performance and stability of the device. Moreover, after low-temperature thermal annealing, the hole mobility of the device can even reach as high as 4.80 cm2 V-1 s-1, and we tested the optical response of the device to the ultraviolet wavelength and found that its maximum optical responsivity was 8.2 AW-1.

Solution-Processable liquid crystalline organic semiconductors based on 6-(Thiophen-2-yl)benzo[b]thiophene for organic thin-film transistors

Liquid crystalline organic semiconductors have garnered significant attention in the realm of organic thin-film transistors (OTFTs) due to their inherent controllability of phase and electrical properties with temperature variations. Typically, liquid crystalline semiconductors possess distinct structures comprising rigid anisotropic cores and flexible chains. Here, we sought to identify liquid crystalline semiconductor materials by appending a thiophene ring and octyl chain to the anisotropic 6-(thiophen-2-yl)benzo[b]thiophene (TBT) backbone. Among the investigated TBT derivatives, the compound featuring additional thiophene ring and octyl chains on both sides exhibited pronounced liquid crystalline characteristics, specifically the SmE phase. The optical, thermal, and electrical characteristics as well as thin film properties of the TBT derivatives were investigated. The TBT compound was employed through solution-shearing as an active layer for top-contact/bottom-gate OTFTs. The liquid-crystalline TBT (2,6-bis(5-octylthiophen-2-yl)benzo[b]thiophene) thin film annealed at low temperature (30 °C) showed hole mobility as high as 0.025 cm2/Vs and current on/off ratio of > 106. This results in a significant enhancement by an order of magnitude compared to the sample annealed at 70 °C in the SmE phase, and nearly a two-fold improvement compared to the performance observed in the sample annealed at 130 °C in the transition phase. The utilization of the TBT derivative as a p-channel material represents a significant step toward the development of novel liquid crystalline semiconductors.

High-performance organic field effect transistor of liquid crystalline organic semiconductor using silver electrodes with bottom-gate top-contact configuration

We have investigated organic field effect transistors (OFETs) fabricated with liquid crystalline organic semiconductor, 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10), and silver (Ag) source-drain electrodes. Ph-BTBT-10 OFETs using Ag source-drain electrodes in bottom-gate top-contact configuration exhibit high mobility of 8.2 cm2 Vs−1, which is similar to those of gold (Au) electrodes. Contact resistance of Ph-BTBT-10 OFETs using Ag electrodes achieved 0.49 kΩcm by transfer length method, which is lower than those of Au electrodes, 2.7 kΩcm. Ph-BTBT-10 OFET using Ag source-drain electrodes in bottom-gate top-contact configuration is a promising candidate for high-performance and low-cost OFETs.

Conformational Change of Alkyl Chains at Phase Transitions in Thin Films of an Asymmetric Benzothienothiophene Derivative.

Among many promising organic semiconducting materials, 2-decyl-7-phenyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C10) shows outstanding device performances for organic field-effect transistors. This compound has a highly ordered liquid crystalline state, i.e., the smectic E (SmE) phase. Although the transition from the crystalline state to the SmE phase is believed to accompany melting of the alkyl chains, no spectroscopic evidence has been found so far. In this study, the conformational change of the decyl chains in Ph-BTBT-C10 films across the phase transition is analyzed by temperature-dependent measurements in situ using infrared spectroscopy. The spectral analysis reveals that the polycrystalline film has latent conformational disorder (the gauche conformer), the rate of which becomes more pronounced with the heat treatment. As expected, melting of the decyl chains is observed above the transition temperature to the SmE phase. This study also highlights the discovery of some key bands sensitive to the phase transitions in liquid crystalline organic semiconductors.

1]Benzothieno[3,2-b][1]benzothiophene-based liquid crystalline organic semiconductor for solution-processed organic thin film transistors

Liquid crystalline organic semiconductors have drawn tremendous interest due to potentials of applications in organic thin-film transistors (OTFTs) with their high electrical performance and solution-processability. However, alkylated liquid crystals often encounter poor thermal durability and mobility drop at smectic E (SmE) phase. Here, we introduce new solution-processable [1]benzothieno[3,2-b][1]benzothiophene-based small molecules with different types of alkyl side chains for OTFTs. All BTBT derivatives showed smectic phase; dialkylated 2-octyl-7-(5′-octyl-[2,2′-bithiophen]-5-yl)benzo[b]benzo[4,5]thieno[2,3-d]thiophene (O-2Th-BTBT) and 2-(5′-(2-ethylhexyl)-[2,2′-bithiophen]-5-yl)-7-octylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (E-2Th-BTBT) suffered mobility degradation at SmE phase. However, monoalkylated 2-([2,2′-bithiophen]-5-yl)-7-octylbenzo[b]benzo[4,5]thieno[2,3-d]thiophene (2Th-BTBT) did not exhibit SmE phase over temperature range, resulting in high carrier mobility up to 0.31 cm2/Vs through molecular bilayer transition by thermal annealing. Physicochemical and liquid crystal properties were analyzed, and thin film characterization by atomic force microscopy and X-ray diffraction was discussed.

Use of doping to achieve low contact resistance in bottom-gate top-contact type organic transistor with liquid-crystalline organic semiconductor, Ph-BTBT-10

We have investigated the characteristics of bottom-gate and top-contact type field effect transistors fabricated with polycrystalline thin films of a liquid-crystalline organic semiconductor, 2-decyl-7-phenyl-benzothienobenzothiophene (Ph-BTBT-10), with a p-type dopant, tetrafluoro-tetracyano-quinodimethane (F4-TCNQ). We found that the contact resistance between the semiconductor and electrode was reduced from 3.0 kΩ cm to 1.2 kΩ cm by contact doping with F4-TCNQ, and to 0.9 kΩcm by subsequent thermal annealing of the films, in which the F4-TCNQ dopant diffused from the surface to the interior of the Ph-BTBT-10 thin film. In addition, we found that contact-doped and thermally annealed devices showed higher mobility and smaller threshold voltage in short-channel devices compared to pristine devices. We conclude that thermal diffusion of dopants to improve FET performance is an important technique.

13 C NMR investigations of molecular order of rod-like, bent-core, and thiophene mesogens.

In this review, methods to obtain the orientational order of topologically variant molecular mesogens using by one- and two-dimensional (2D) solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy are described. Besides 13 C chemical shifts, the 13 C─1 H dipolar couplings measured from 2D-separated local field (SLF) technique are used for computing the order parameters of a variety of mesogens. The investigated molecules are composed of a variable number of rings in the core, that is, core ranging from simply one ring to five rings. Among the mesogens investigated, a special focus has been placed on mesogens with thiophene rings, which are gaining popularity as liquid crystalline organic semiconductors. The replacement of a phenyl ring by thiophene in the core has a dramatic influence on molecular topology, as observed from the measured order parameters. The review highlights the advantages of the 2D SLF method for understanding the local dynamics and for mapping the topology of mesogens through the measured order parameters. SLF NMR studies of as many as 24 molecular mesogens that vary in terms of the molecular structure as well as topology are covered in the review. Order parameters of the rings have been estimated from the 13 C─1 H dipolar couplings in the nematic, smectic A, smectic C, and tilted hexatic phases as well as in B1 and B2 mesophases of various mesogens. It is anticipated that, in the years to come, the 2D SLF method would provide advanced molecular information on structurally complex mesogens that are emerging in liquid crystal science through the incessant efforts of synthetic chemists. The mini review covers the orientational order of topologically variant molecular mesogens determined by 1D and 2D solid-state 13 C NMR spectroscopy. Accordingly, rod-like, bent-core, and thiophene mesogens were subjected to 2D SLF measurements to get the order parameters from which the topology was established. The replacement of phenyl ring by thiophene and its influence on order parameters as well as on molecular topology is also discussed.

Characteristic and Molecular Design of Liquid Crystalline Organic Semiconductors as Organic Transistor Materials

Characteristic and Molecular Design of Liquid Crystalline Organic Semiconductors as Organic Transistor Materials

Novel calamitic liquid crystalline organic semiconductors based on electron-deficient dibenzo[c,h][2,6]naphthyridine: synthesis, mesophase, and charge transport properties by the time-of-flight technique

Mobility shows Poole–Frenkel like behaviour in the low order mesophase of liquid crystalline organic semiconductors based on an electron-deficient dibenzo[c,h][2,6]naphthyridine (DBN) derivative.

Tuning charge carrier transport and optical birefringence in liquid-crystalline thin films: A new design space for organic light-emitting diodes

Liquid-crystalline organic semiconductors exhibit unique properties that make them highly interesting for organic optoelectronic applications. Their optical and electrical anisotropies and the possibility to control the alignment of the liquid-crystalline semiconductor allow not only to optimize charge carrier transport, but to tune the optical property of organic thin-film devices as well. In this study, the molecular orientation in a liquid-crystalline semiconductor film is tuned by a novel blading process as well as by different annealing protocols. The altered alignment is verified by cross-polarized optical microscopy and spectroscopic ellipsometry. It is shown that a change in alignment of the liquid-crystalline semiconductor improves charge transport in single charge carrier devices profoundly. Comparing the current-voltage characteristics of single charge carrier devices with simulations shows an excellent agreement and from this an in-depth understanding of single charge carrier transport in two-terminal devices is obtained. Finally, p-i-n type organic light-emitting diodes (OLEDs) compatible with vacuum processing techniques used in state-of-the-art OLEDs are demonstrated employing liquid-crystalline host matrix in the emission layer.

Observations of cavity polaritons in one-dimensional photonic crystals containing a liquid-crystalline semiconductor based on perylene bisimide units.

We investigated the optical transmission properties of one-dimensional photonic crystal (1D-PC) microcavity structures containing the liquid-crystalline (LC) perylene tetracarboxylic bisimide (PTCBI) derivative. We fabricated the microcavity structures for this study by two different methods and observed the cavity polaritons successfully in both samples. For one sample, since the PTCBI molecules were aligned in the cavity layer of the 1D-PC by utilizing a friction transfer method, vacuum Rabi splitting energy was strongly dependent on the polarization of the incident light produced by the peculiar optical features of the LC organic semiconductor. For the other sample, we did not utilize the friction transfer method and did not observe such polarization dependence. However, we did observe a relatively large Rabi splitting energy of 187 meV, probably due to the improvement of optical confinement effect.

Planar-orientation polycrystalline thin film of liquid-crystalline organic semiconductor by template-directed self-assembly

We fabricated planar-orientation crystalline thin films of organic semiconductors, in which molecules sit parallel, i.e., “face-on”, on the substrate and favor vertical charge transport. Thanks to molecular orientation that is sensitive to surface properties and the self-organization of liquid crystals, planar-orientation crystalline thin films can be prepared by simply cooling a smectic liquid-crystalline organic semiconductor from isotropic temperature with the aid of a poly(vinyl alcohol) (PVA) microtemplate. The molecular orientation of crystalline thin films was investigated by polarized optical microscopy (POM) and X-ray diffraction (XRD) analysis, and the current–voltage characteristics of the films were studied in a diode configuration. The results showed high potential for device applications.

Liquid crystal and crystal structures of a phenyl-benzothienobenzothiophene derivative

ABSTRACTWe have investigated liquid crystal and crystal structures of a smectic E (SmE) liquid crystalline organic-semiconductor, 2-decyl-7-phenyl-benzothienobenzothiophene (Ph-BTBT-10). X-ray diffraction study revealed that the bulk and thin film crystals prepared from SmE phase exhibited the herringbones structure within molecular layer of ab-plane, which inherited from the SmE phase, and that the crystal structure of these crystals were almost same as that of single crystal. The high mobility in field effect transistors fabricated with crystalline thin films of Ph-BTBT-10 was discussed in relation to the transfer integral estimated from the lattice structure of single crystal of Ph-BTBT-10.

A Solution-Processable Liquid-Crystalline Semiconductor for Low-Temperature-Annealed Air-Stable N-Channel Field-Effect Transistors.

A new solution-processable and air-stable liquid-crystalline n-channel organic semiconductor (2,2'-(2,8-bis(5-(2-octyldodecyl)thiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile, α,ω-2OD-TIFDMT) with donor-acceptor-donor (D-A-D) π conjugation has been designed, synthesized, and fully characterized. The new semiconductor exhibits a low LUMO energy (-4.19 eV) and a narrow optical bandgap (1.35 eV). The typical pseudo-focal-conic fan-shaped texture of a hexagonal columnar liquid-crystalline (LC) phase was observed over a wide temperature range. The spin-coated semiconductor thin films show the formation of large (≈0.5-1 μm) and highly crystalline platelike grains with edge-on molecular orientations. Low-temperature-annealed (50 °C) top-contact/bottom-gate OFETs have provided good electron mobility values as high as 0.11 cm2 (V s)-1 and high Ion /Ioff ratios of 107 to 108 with excellent ambient stability. This indicates an enhancement of two orders of magnitude (100×) when compared with the β-substituted parent semiconductor, β-DD-TIFDMT (2,2'-(2,8-bis(3-dodecylthiophen-2-yl)indeno[1,2-b]fluorene-6,12-diylidene)dimalononitrile). The current rational alkyl-chain engineering route offers great advantages for D-A-D π-core coplanarity in addition to maintaining good solubility in organic solvents, and leads to favorable optoelectronic/physicochemical characteristics. These remarkable findings demonstrate that α,ω-2OD-TIFDMT is a promising semiconductor material for the development of n-channel OFETs on flexible plastic substrates and LC-state annealing of the columnar liquid crystals can lower the electron mobility for transistor-type charge transport.

Plasmonic Nanospectroscopy for Thermal Analysis of Organic Semiconductor Thin Films.

Organic semiconductors are key materials for the next generation thin film electronic devices like field-effect transistors, light-emitting diodes, and solar cells. Accurate thermal analysis is essential for the fundamental understanding of these materials, for device design, stability studies, and quality control because the desired nanostructures are often far from thermodynamic equilibrium and therefore tend to evolve with time and temperature. However, classical experimental techniques are insufficient because the active layer of most organoelectronic device architectures is typically only on the order of a hundred nanometers or less. Scrutinizing the thermal properties in this size range is, however, critical because strong deviations of the thermal properties from bulk values due to confinement effects and pronounced influence of the substrate become significant. Here, we introduce plasmonic nanospectroscopy as an experimental approach to scrutinize the thickness dependence of the thermal stability of semicrystalline, liquid-crystalline, and glassy organic semiconductor thin films down to the sub-100 nm film thickness regime. In summary, we find a pronounced thickness dependence of the glass transition temperature of ternary polymer/fullerene blend thin films and their constituents, which can be resolved with exceptional precision by the plasmonic nanospectroscopy method, which relies on remarkably simple instrumentation.

A new development for liquid crystalline organic semiconductors

A new development for liquid crystalline organic semiconductors

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.

Liquid crystalline organic semiconductors for organic transistor applications

Liquid crystalline organic semiconductors are good candidates for organic transistors because the materials have properties that are beneficial compared with those of polymer materials. Liquid crystalline materials show good solution processability for the fabrication of uniform crystalline thin films. The novel liquid crystalline material 2-phenyl-7-decyl[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-10) exhibits a highly ordered liquid crystal phase, and has good solution processability and high thermal durability to use for creating transistor devices with high mobility, over 10 cm2 Vs−1, following thermal annealing.

The effect of thermal annealing on the layered structure of smectic liquid crystalline organic semiconductor on polyimide gate insulator and its OFET performance

The electrical performance of organic field-effect transistors (OFETs) depends on the quality of thin-film organic semiconductors, which is significantly affected by solution-processing conditions and additional processes. We investigated the effects of post-thermal annealing on the thin-film morphologies of liquid crystalline organic semiconductors on polyimide gate insulator surface and the FET performances of the films. The active material selected for the OFETs was 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene (Ph-BTBT-C10), which shows a highly ordered smectic E (SmE) mesophase and polycrystalline thin films feature very high mobility. We aimed to produce well defined molecular orientation and crystal structure in thin-film Ph-BTBT-C10 on polyimide gate insulator not typical SiO2 gate insulator via thermal annealing process. Uniform bilayer- or monolayer-structured polycrystalline thin films were obtained on polymer gate insulator after thermal annealing at a SmE (over 148°C) and SmA (over 213°C) liquid crystalline phase temperature, respectively. The OFET using bilayer-structured thin film showed high performance with a mobility of 2.27cm2/Vs.