2D organic semiconductor crystals are emerging as a fascinating platform with regard to their applications in organic field-effect transistors (OFETs), attributed to their enhanced charge transport efficiency and their new optoelectronic functions, based on their unique morphological features. Advances in material processing techniques have not only enabled easy fabrication of few-monolayered 2D nanostructures but also facilitated exploration of the interesting properties induced by characteristic 2D morphologies. However, to date, only a limited number of representative organic semiconductors have been utilized in organic 2D optoelectronics. Therefore, in order to further spur this research, an intuitive crystal engineering principle for realizing organic 2D crystals is required. In this regard, here, not only the important implications of applying 2D structures to OFET devices are discussed but also a crystal engineering protocol is provided that first predicts molecular arrangements depending on the molecular factors, which is followed by realizing 2D supramolecular synthon networks for different molecular packing motifs. It is expected that 2D organic semiconductor crystals developed by this approach will pave a promising way toward next-generation organic 2D optoelectronics.

Organic 2D Optoelectronic Crystals: Charge Transport, Emerging Functions, and Their Design Perspective

The increase in demand and popularity of smart textiles brings new and innovative ideas to develop a diverse range of textile-based devices for our daily life applications. Smart textile-based sensors (TEX sensors) become attractive due to the potential to replace current solid-state sensor devices with flexible and wearable devices. We have developed a smart textile sensor for humidity detection using a metal-organic framework (MOF) as an active thin-film layer. We show for the first time the use of the Langmuir-Blodgett (LB) technique for the deposition of a MIL-96(Al) MOF thin film directly onto the fabrics containing interdigitated textile electrodes for the fabrication of a highly selective humidity sensor. The humidity sensors were made from two different types of textiles, namely, linen and cotton, with the linen-based sensor giving the best response due to better coverage of MOF. The TEX sensor showed a reproducible response after multiple cycles of measurements. After 3 weeks of storage, the sensor showed a moderate decrease in response. Moreover, TEX sensors showed a high level of selectivity for the detection of water vapors in the presence of several volatile organic compounds (VOCs). Interestingly, the selectivity is superior to some of the previously reported MOF-coated solid-state interdigitated electrode devices and textile sensors. The method herein described is generic and can be extended to other textiles and coating materials for the detection of toxic gases and vapors.

/pdf/highly-selective-metal-organic-framework-textile-humidity-g25ajafk5f.pdf

Highly Selective Metal–Organic Framework Textile Humidity Sensor

A new strategy for the efficient synthesis of thieno[3,2-b]benzofuran derivatives (15 examples) was achieved on the basis of successive regioselective intermolecular Suzuki and newly developed intramolecular Ullmann C-O reactions in up to a 70% overall yield. The fast intramolecular C-O reaction can be realized by an efficient catalytic combination of CuI/1,10-phenanthroline in up to a 97% yield. This method is suitable for the construction of highly fused thieno[3,2-b]furan-containing heterocycles including DTBDF and TTDBF. The π-π and hydrogen-bonding interactions observed for the C8-DTBDF single crystal suggest its great potential for OFET applications in the near future.

Ullmann-Type Intramolecular C–O Reaction Toward Thieno[3,2-b]furan Derivatives with up to Six Fused Rings

The structural, electro-optical, charge transport and nonlinear optical properties of 2-[(3,5-dimethyl-1-phenyl-1H-pyrazol-4-yl)methylidene]indan-1,3-dione

Organic thin film transistor (OTFT) based gas sensors have demonstrated promising applications, owing to their advantages of high selectivity and room temperature operation, accompanied by their low cost, large scale manufacture, and flexibility. However, the understanding of the sensing mechanism is far from clear. Herein, we reveal the sensing mechanism of an organic transistor sensor for ammonia (NH3) detection through studying the recovery behavior in various atmospheres. Inspired by the significant difference in the recovery of the transistor sensor in N2 and in air, we deduced that the operation mechanism should not only involve the NH3–film interaction. Among a series of recovery processes, only upon exposure to wet air can the sensors completely recover in a certain time. Such a phenomenon, coupled with the transistor’s performance evolution under vacuum, directly evidenced the existence of a pre-doping effect in the transistor by water (H2O) in ambient air. As a result, the response to the NH3 analyte is actually a de-doping process via reaction with the H2O. The full recovery in wet air is attributable to re-doping by H2O. Density functional theory (DFT) calculations were employed to assist the understanding of such a sensing mechanism. This study could help in the understanding of the sensing processes in many organic semiconductor based sensors.

An ammonia detecting mechanism for organic transistors as revealed by their recovery processes

Increased interest in wearable and smart electronics is driving numerous research works on organic electronics. The control of film growth and patterning is of great importance when targeting high-performance organic semiconductor devices. In this Feature Article, we summarize our recent work focusing on the growth, crystallization, and device operation of organic semiconductors intermediated by ultrathin organic films (in most cases, only a monolayer). The site-selective growth, modified crystallization and morphology, and improved device performance of organic semiconductor films are demonstrated with the help of the inducing layers, including patterned and uniform Langmuir–Blodgett monolayers, crystalline ultrathin organic films, and self-assembled polymer brush films. The introduction of the inducing layers could dramatically change the diffusion of the organic semiconductors on the surface and the interactions between the active layer with the inducing layer, leading to improved aggregation/crystalli...

Monolayer-Mediated Growth of Organic Semiconductor Films with Improved Device Performance.

Introducing foreign particles or agents as nucleator is an efficient way to promote crystallization in the crystal growth field, with the advantage to speed up the crystallizing rate and control the growth process. However, in the field of organic crystalline film growth, where the crystallization and morphology modulation are of significant importance in optoelectronics, this method has rarely been utilized. Particularly, some potential high-performance materials such as rubrene face the problem of crystallization during film formation. Here a strategy is reported to promote the crystallization of rubrene films in the initial stage assisted by foreign particles. Highly ordered thin film from the sub-monolayer stage can be achieved. Efficient charge transport and high mobility up to 2.95 cm(2) V(-1) s(-1) are achieved on thus ultrathin crystalline films. Such a method enables the well controlling of the film growth from the very early stage and produces uniform crystalline films with good reproducibility, thus highly promising to yield desired optoelectrical properties and applications.

Foreign Particle Promoted Crystalline Nucleation for Growing High-Quality Ultrathin Rubrene Films.

The growth of organic semiconductor with controllable morphology is a crucial issue for achieving high-performance devices. Here we present the systematic study of the effect of the alkyl chain attached to the functional entity on controlling the growth of oriented microcrystals by dip-coating. Alkylated DTBDT-based molecules with variable chain lengths from n-butyl to n-dodecyl formed into one-dimensional micro- or nanostripe crystals at different pulling speeds. The alignment and ordering are significantly varied with alkyl chain length, as is the transistor performance. Highly uniform oriented and higher-molecular-order crystalline stripes with improved field-effect mobility can be achieved with an alkyl-chain length of around 6. We attribute this effect to the alkyl-chain-length-dependent packing, solubility, and self-assembly behavior.

Growth of Highly Oriented Ultrathin Crystalline Organic Microstripes: Effect of Alkyl Chain Length

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Papers

Monolayer-Mediated Growth of Organic Semiconductor Films with Improved Device Performance.

Foreign Particle Promoted Crystalline Nucleation for Growing High-Quality Ultrathin Rubrene Films.

Growth of Highly Oriented Ultrathin Crystalline Organic Microstripes: Effect of Alkyl Chain Length