液晶物質の有機トランジスタへの展開 ; Liquid Crystals for Organic Thin Film Transistors
01 Jan 2017-
TL;DR: In this article, a liquid crystal phase of smectic E (SmE) was used to solve inhomogeneity and poor thermal durability of polycrystalline thin films of organic semiconductors.
Abstract: 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 cm2 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.
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TL;DR: The article reviews the current understanding of the physical mechanisms that determine the (opto)electronic properties of high-performance organic materials and highlights the capabilities of various experimental techniques for characterization, summarizes top-of-the-line device performance, and outlines recent trends in the further development of the field.
Abstract: Organic (opto)electronic materials have received considerable attention due to their applications in thin-film-transistors, light-emitting diodes, solar cells, sensors, photorefractive devices, and many others. The technological promises include low cost of these materials and the possibility of their room-temperature deposition from solution on large-area and/or flexible substrates. The article reviews the current understanding of the physical mechanisms that determine the (opto)electronic properties of high-performance organic materials. The focus of the review is on photoinduced processes and on electronic properties important for optoelectronic applications relying on charge carrier photogeneration. Additionally, it highlights the capabilities of various experimental techniques for characterization of these materials, summarizes top-of-the-line device performance, and outlines recent trends in the further development of the field. The properties of materials based both on small molecules and on conjug...
995 citations
TL;DR: This Review discusses current understanding of charge carrier transport in conjugated polymers and small molecule semiconductors and strategies to improve their performance.
Abstract: Conjugated polymers and molecular semiconductors are emerging as a viable semiconductor technology in industries such as displays, electronics, renewable energy, sensing and healthcare. A key enabling factor has been significant scientific progress in improving their charge transport properties and carrier mobilities, which has been made possible by a better understanding of the molecular structure–property relationships and the underpinning charge transport physics. Here we aim to present a coherent review of how we understand charge transport in these high-mobility van der Waals bonded semiconductors. Specific questions of interest include estimates for intrinsic limits to the carrier mobilities that might ultimately be achievable; a discussion of the coupling between charge and structural dynamics; the importance of molecular conformations and mesoscale structural features; how the transport physics of conjugated polymers and small molecule semiconductors are related; and how the incorporation of counterions in doped films—as used, for example, in bioelectronics and thermoelectric devices—affects the electronic structure and charge transport properties. Organic semiconductors are making their way into applications ranging from display technology to flexible electronics and biomedical applications. This Review discusses current understanding of charge carrier transport in these materials and strategies to improve their performance.
408 citations
TL;DR: In this article, the design of liquid-crystalline phases, the resultant self-assembled structures, the transport mechanisms, and the fabrication, function and future development of devices incorporating nanostructured liquid crystals are described.
Abstract: The nanosegregated structures of columnar, smectic and bicontinuous cubic liquid crystals can provide well-organized, nano- and sub-nanosized 1D, 2D and 3D channels capable of ion and electron transport. The molecular shape, intermolecular interactions and nanosegregation of the molecular structures can influence their self-assembly into a range of functional liquid-crystalline nanostructures. The formation of stable and soft liquid-crystalline materials leads to their application as electrolytes for batteries and photovoltaics, semiconductors, electroluminescence and electrochemical devices. In addition, electrochemical devices are obtained by using redox-active liquid crystals. In this Review, we focus on the design of liquid-crystalline phases, the resultant self-assembled structures, the transport mechanisms, and the fabrication, function and future development of devices incorporating nanostructured liquid crystals. Liquid-crystalline nanostructures can form well-organized 1D, 2D and 3D channels capable of transporting ions or electrons. In this Review, the design of liquid-crystalline phases, their self-assembled structures, and the fabrication and function of devices incorporating them are described.
292 citations
TL;DR: Herein, the applications of organic 2D materials for optoelectronic devices are a main focus and an introduction to what is known and suggestions for the potential of many exciting developments are presented.
Abstract: The remarkable merits of 2D materials with atomically thin structures and optoelectronic attributes have inspired great interest in integrating 2D materials into electronics and optoelectronics. Moreover, as an emerging field in the 2D-materials family, assembly of organic nanostructures into 2D forms offers the advantages of molecular diversity, intrinsic flexibility, ease of processing, light weight, and so on, providing an exciting prospect for optoelectronic applications. Herein, the applications of organic 2D materials for optoelectronic devices are a main focus. Material examples include 2D, organic, crystalline, small molecules, polymers, self-assembly monolayers, and covalent organic frameworks. The protocols for 2D-organic-crystal-fabrication and -patterning techniques are briefly discussed, then applications in optoelectronic devices are introduced in detail. Overall, an introduction to what is known and suggestions for the potential of many exciting developments are presented.
255 citations
TL;DR: The main focus of this report is on obtaining printed electrodes with high-resolution patterning and the electrical performance of printed TFTs using such printed electrodes.
Abstract: Printed electronics enable the fabrication of large-scale, low-cost electronic devices and systems, and thus offer significant possibilities in terms of developing new electronics/optics applications in various fields. Almost all electronic applications require information processing using logic circuits. Hence, realizing the high-speed operation of logic circuits is also important for printed devices. This report summarizes recent progress in the development of printed thin-film transistors (TFTs) and integrated circuits in terms of materials, printing technologies, and applications. The first part of this report gives an overview of the development of functional inks such as semiconductors, electrodes, and dielectrics. The second part discusses high-resolution printing technologies and strategies to enable high-resolution patterning. The main focus of this report is on obtaining printed electrodes with high-resolution patterning and the electrical performance of printed TFTs using such printed electrodes. In the final part, some applications of printed electronics are introduced to exemplify their potential.
245 citations
References
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TL;DR: In this article, the authors used thin-film, field effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT.
Abstract: Self-organization in many solution-processed, semiconducting conjugated polymers results in complex microstructures, in which ordered microcrystalline domains are embedded in an amorphous matrix1. This has important consequences for electrical properties of these materials: charge transport is usually limited by the most difficult hopping processes and is therefore dominated by the disordered matrix, resulting in low charge-carrier mobilities2 (⩽10-5 cm2 V-1 s-1). Here we use thin-film, field-effect transistor structures to probe the transport properties of the ordered microcrystalline domains in the conjugated polymer poly(3-hexylthiophene), P3HT. Self-organization in P3HT results in a lamella structure with two-dimensional conjugated sheets formed by interchain stacking. We find that, depending on processing conditions, the lamellae can adopt two different orientations—parallel and normal to the substrate—the mobilities of which differ by more than a factor of 100, and can reach values as high as 0.1 cm2 V-1 s-1 (refs 3, 4). Optical spectroscopy of the field-induced charge, combined with the mobility anisotropy, reveals the two-dimensional interchain character of the polaronic charge carriers, which exhibit lower relaxation energies than the corresponding radical cations on isolated one-dimensional chains. The possibility of achieving high mobilities via two-dimensional transport in self-organized conjugated lamellae is important for applications of polymer transistors in logic circuits5 and active-matrix displays4,6.
4,306 citations
TL;DR: New semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers are reported on, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices.
Abstract: Organic semiconductors that can be fabricated by simple processing techniques and possess excellent electrical performance, are key requirements in the progress of organic electronics. Both high semiconductor charge-carrier mobility, optimized through understanding and control of the semiconductor microstructure, and stability of the semiconductor to ambient electrochemical oxidative processes are required. We report on new semiconducting liquid-crystalline thieno[3,2-b ]thiophene polymers, the enhancement in charge-carrier mobility achieved through highly organized morphology from processing in the mesophase, and the effects of exposure to both ambient and low-humidity air on the performance of transistor devices. Relatively large crystalline domain sizes on the length scale of lithographically accessible channel lengths (∼200 nm) were exhibited in thin films, thus offering the potential for fabrication of single-crystal polymer transistors. Good transistor stability under static storage and operation in a low-humidity air environment was demonstrated, with charge-carrier field-effect mobilities of 0.2–0.6 cm2 V−1 s−1 achieved under nitrogen.
2,011 citations
TL;DR: It is shown that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces.
Abstract: Printing electronic devices using semiconducting 'ink' is seen as a promising route to cheap, large-area and flexible electronics, but the performance of such devices suffers from the relatively poor crystallinity of the printed material. Hiromi Minemawari and colleagues have developed an inkjet-based printing technique involving controlled mixing on a surface of two solutions — the semiconductor (C8-BTBT) in its solvent and a liquid in which the semiconductor is insoluble. The products of this antisolvent crystallization technique are thin semiconductor films with exceptionally high and uniform crystallinity. The use of single crystals has been fundamental to the development of semiconductor microelectronics and solid-state science1. Whether based on inorganic2,3,4,5 or organic6,7,8 materials, the devices that show the highest performance rely on single-crystal interfaces, with their nearly perfect translational symmetry and exceptionally high chemical purity. Attention has recently been focused on developing simple ways of producing electronic devices by means of printing technologies. ‘Printed electronics’ is being explored for the manufacture of large-area and flexible electronic devices by the patterned application of functional inks containing soluble or dispersed semiconducting materials9,10,11. However, because of the strong self-organizing tendency of the deposited materials12,13, the production of semiconducting thin films of high crystallinity (indispensable for realizing high carrier mobility) may be incompatible with conventional printing processes. Here we develop a method that combines the technique of antisolvent crystallization14 with inkjet printing to produce organic semiconducting thin films of high crystallinity. Specifically, we show that mixing fine droplets of an antisolvent and a solution of an active semiconducting component within a confined area on an amorphous substrate can trigger the controlled formation of exceptionally uniform single-crystal or polycrystalline thin films that grow at the liquid–air interfaces. Using this approach, we have printed single crystals of the organic semiconductor 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) (ref. 15), yielding thin-film transistors with average carrier mobilities as high as 16.4 cm2 V−1 s−1. This printing technique constitutes a major step towards the use of high-performance single-crystal semiconductor devices for large-area and flexible electronics applications.
1,505 citations
TL;DR: The growth of a highly aligned meta-stable structure of 2,7-dioctyl[1]benzothieno[3,2-b][1] Benzothiophene (C8-BTBT) is described from a blended solution of C8- BTBT and polystyrene by using a novel off-centre spin-coating method, indicating their potential for transparent, high-performance organic electronics.
Abstract: One of the advantages of organic over inorganic semiconductors is they can be grown from solution, but their electrical mobility is often poor. Yuan et al. report a technique for fabricating organic transistors with mobilities far beyond that of amorphous silicon and close to that of polycrystalline silicon.
1,130 citations
TL;DR: The air-gap field-effect technique enabled realization of the intrinsic (not limited by static disorder) polaronic transport on the surface of rubrene (C42H28) crystals over a wide temperature range.
Abstract: The air-gap field-effect technique enabled realization of the intrinsic (not limited by static disorder) polaronic transport on the surface of rubrene (C42H28) crystals over a wide temperature range. The signatures of this intrinsic transport are the anisotropy of the carrier mobility, mu, and the growth of mu with cooling. Anisotropy of mu vanishes in the activation regime at low temperatures, where the transport is dominated by shallow traps. The deep traps, introduced by x-ray radiation, increase the field-effect threshold without affecting mu, an indication that the filled traps do not scatter polarons.
1,087 citations