Low-Temperature Alignment of Conjugated Polymers by Plasticizer-Aided Physical Rubbing.

Rubbing-induced alignment of conjugated polymers is systematically investigated in terms of intra- and inter-molecular interaction. Various polymer films with a broad range of polymer chain rigidity are rubbed, and the degree of polymer chain alignment is quantitatively characterized. The rubbing technique effectively aligns crystalline domains in conjugated polymer films when the temperature approaches the critical rubbing temperature ( T r c $T_{\mathrm{r}}^{\mathrm{c}}$ ), at which the rearrangement and the slip of polymer chains are possible. A polymer with significant intra-/inter-molecular interactions exhibits higher T r c $T_{\mathrm{r}}^{\mathrm{c}}$ , though quantitative analysis reveals an intermediately aligned state at temperature Tr ' lower than T r c $T_{\mathrm{r}}^{\mathrm{c}}$ . This state originates from polymer chain aggregation in an amorphous domain. The intermediately aligned state can be controlled by plasticizer, which enables low-temperature alignment of high-mobility polymer film by reducing Tr ' to near 100 °C, increases the crystallinity, and improves the alignment effect at this state comparable to that of the completely aligned state obtained at extremely high temperatures.

Tailored Uniaxial Alignment of Nanowires Based on Off-Center Spin-Coating for Flexible and Transparent Field-Effect Transistors.

The alignment of nanowires (NWs) has been actively pursued for the production of electrical devices with high-operating performances. Among the generally available alignment processes, spin-coating is the simplest and fastest method for uniformly patterning the NWs. During spinning, the morphology of the aligned NWs is sensitively influenced by the resultant external drag and inertial forces. Herein, the assembly of highly and uniaxially aligned silicon nanowires (Si NWs) is achieved by introducing an off-center spin-coating method in which the applied external forces are modulated by positioning the target substrate away from the center of rotation. In addition, various influencing factors, such as the type of solvent, the spin acceleration time, the distance between the substrate and the center of rotation, and the surface energy of the substrate, are adjusted in order to optimize the alignment of the NWs. Next, a field-effect transistor (FET) incorporating the highly aligned Si NWs exhibits a high effective mobility of up to 85.7 cm2 V-1 s-1, and an on-current of 0.58 µA. Finally, the single device is enlarged and developed in order to obtain an ultrathin and flexible Si NW FET array. The resulting device has the potential to be widely expanded into applications such as wearable electronics and robotic systems.

Anisotropy of Charge Transport in a Uniaxially Aligned Fused Electron-Deficient Polymer Processed by Solution Shear Coating.

Precise control of the microstructure in organic semiconductors (OSCs) is essential for developing high-performance organic electronic devices. Here, a comprehensive charge transport characterization of two recently reported rigid-rod conjugated polymers that do not contain single bonds in the main chain is reported. It is demonstrated that the molecular design of the polymer makes it possible to achieve an extended linear backbone structure, which can be directly visualized by high-resolution scanning tunneling microscopy (STM). The rigid structure of the polymers allows the formation of thin films with uniaxially aligned polymer chains by using a simple one-step solution-shear/bar coating technique. These aligned films show a high optical anisotropy with a dichroic ratio of up to a factor of 6. Transport measurements performed using top-gate bottom-contact field-effect transistors exhibit a high saturation electron mobility of 0.2 cm2 V-1 s-1 along the alignment direction, which is more than six times higher than the value reported in the previous work. This work demonstrates that this new class of polymers is able to achieve mobility values comparable to state-of-the-art n-type polymers and identifies an effective processing strategy for this class of rigid-rod polymer system to optimize their charge transport properties.

Charge-Transfer-Controlled Growth of Organic Semiconductor Crystals on Graphene.

Controlling the growth behavior of organic semiconductors (OSCs) is essential because it determines their optoelectronic properties. In order to accomplish this, graphene templates with electronic-state tunability are used to affect the growth of OSCs by controlling the van der Waals interaction between OSC ad-molecules and graphene. However, in many graphene-molecule systems, the charge transfer between an ad-molecule and a graphene template causes another important interaction. This charge-transfer-induced interaction is never considered in the growth scheme of OSCs. Here, the effects of charge transfer on the formation of graphene-OSC heterostructures are investigated, using fullerene (C60) as a model compound. By in situ electrical doping of a graphene template to suppress the charge transfer between C60 ad-molecules and graphene, the layer-by-layer growth of a C60 film on graphene can be achieved. Under this condition, the graphene-C60 interface is free of Fermi-level pinning; thus, barristors fabricated on the graphene-C60 interface show a nearly ideal Schottky-Mott limit with efficient modulation of the charge-injection barrier. Moreover, the optimized C60 film exhibits a high field-effect electron mobility of 2.5 cm2 V-1 s-1. These results provide an efficient route to engineering highly efficient optoelectronic graphene-OSC hybrid material applications.

Motion-Programmed Bar-Coating Method with Controlled Gap for High-Speed Scalable Preparation of Highly Crystalline Organic Semiconductor Thin Films.

Solution-processed organic semiconductor thin films with high charge carrier mobility are necessary for development of next-generation electronic applications, but the rapid processing speed demanded for the industrial-scale production of these thin films poses a challenge to control of their thin-film properties, such as crystallinity, morphology, and film-to-film uniformity. Here, we show a new solution coating method that is compatible with a roll-to-roll printing process at a rate of 2 mm s-1 by using a gap-controllable wire bar, motion-programming strategy, and blended active inks. We demonstrate that the coating bar, the horizontal motion of which is repeatedly brought to an intermittent standstill, results in an improved vertically self-stratified structure and a high crystallinity for organic active inks comprising a semiconducting small molecule and a semiconducting polymer. Furthermore, organic transistors prepared by the developed method show superior hole mobility with high operational stability (hysteresis and kink-free transfer characteristics), high uniformity over a large area of a 4 in. wafer, good reproducibility, and superior electromechanical stabilities on a flexible plastic substrate. The bar-coating approach demonstrated here will be a step toward developing industrial-scale practical organic electronics applications.

Negative Transconductance Heterojunction Organic Transistors and their Application to Full-Swing Ternary Circuits.

Multivalued logic (MVL) computing could provide bit density beyond that of Boolean logic. Unlike conventional transistors, heterojunction transistors (H-TRs) exhibit negative transconductance (NTC) regions. Using the NTC characteristics of H-TRs, ternary inverters have recently been demonstrated. However, they have shown incomplete inverter characteristics; the output voltage (VOUT ) does not fully swing from VDD to GND . A new H-TR device structure that consists of a dinaphtho[2,3-b:2',3'-f]thieno[3,2-b]thiophene (DNTT) layer stacked on a PTCDI-C13 layer is presented. Due to the continuous DNTT layer from source to drain, the proposed device exhibits novel switching behavior: p-type off/p-type subthreshold region /NTC/ p-type on. As a result, it has a very high on/off current ratio (≈105 ) and exhibits NTC behavior. It is also demonstrated that an array of 36 of these H-TRs have 100% yield, a uniform on/off current ratio, and uniform NTC characteristics. Furthermore, the proposed ternary inverter exhibits full VDD -to-GND swing of VOUT with three distinct logic states. The proposed transistors and inverters exhibit hysteresis-free operation due to the use of a hydrophobic gate dielectric and encapsulating layers. Based on this, the transient operation of a ternary inverter circuit is demonstrated for the first time.

Bar-Coated Ultrathin Semiconductors from Polymer Blend for One-Step Organic Field-Effect Transistors.

One-step deposition of bi-functional semiconductor-dielectric layers for organic field-effect transistors (OFETs) is an effective way to simplify the device fabrication. However, the proposed method has rarely been reported in large-area flexible organic electronics. Herein, we demonstrate wafer-scale OFETs by bar coating the semiconducting and insulating polymer blend solution in one-step. The semiconducting polymer poly(3-hexylthiophene) (P3HT) segregates on top of the blend film, whereas dielectric polymethyl methacrylate (PMMA) acts as the bottom layer, which is achieved by a vertical phase separation structure. The morphology of blend film can be controlled by varying the concentration of P3HT and PMMA solutions. The wafer-scale one-step OFETs, with a continuous ultrathin P3HT film of 2.7 nm, exhibit high electrical reproducibility and uniformity. The one-step OFETs extend to substrate-free arrays that can be attached everywhere on varying substrates. In addition, because of the well-ordered molecular arrangement, the moderate charge transport pathway is formed, which resulted in stable OFETs under various organic solvent vapors and lights of different wavelengths. The results demonstrate that the one-step OFETs have promising potential in the field of large-area organic wearable electronics.

Nanopatched Graphene with Molecular Self-Assembly Toward Graphene-Organic Hybrid Soft Electronics.

Increasing the mechanical durability of large-area polycrystalline single-atom-thick materials is a necessary step toward the development of practical and reliable soft electronics based on these materials. Here, it is shown that the surface assembly of organosilane by weak epitaxy forms nanometer-thick organic patches on a monolayer graphene surface and dramatically increases the material's resistance to harsh postprocessing environments, thereby increasing the number of ways in which graphene can be processed. The nanopatched graphene with the improved mechanical durability enables stable operation when used as transparent electrodes of wearable strain sensors. Also, the nanopatched graphene applied as an electrode modulates the molecular orientation of deposited organic semiconductor layers, and yields favorable nominal charge injection for organic transistors. These results demonstrate the potential for use of self-assembled organic nanopatches in graphene-based soft electronics.

Chemical Vapor Deposition of Bernal-Stacked Graphene on a Cu Surface by Breaking the Carbon Solubility Symmetry in Cu Foils.

The synthesis of Bernal-stacked multilayer graphene over large areas is intensively investigated due to the value of this material's tunable electronic structure, which makes it promising for use in a wide range of optoelectronic applications. Multilayer graphene is typically formed via chemical vapor deposition onto a metal catalyst, such as Ni, a Cu-Ni alloy, or a Cu pocket. These methods, however, require sophisticated control over the process parameters, which limits the process reproducibility and reliability. Here, a new synthetic method for the facile growth of large-area Bernal-stacked multilayer graphene with precise layer control is proposed. A thin Ni film is deposited onto the back side of a Cu foil to induce controlled diffusion of carbon atoms through bulk Cu from the back to the front. The resulting multilayer graphene exhibits a 97% uniformity and a sheet resistance of 50 Ω sq-1 with a 90% transmittance after doping. The growth mechanism is elucidated and a generalized kinetic model is developed to describe Bernal-stacked multilayer graphene growth by the carbon atoms diffused through bulk Cu.

Side-Chain-Induced Rigid Backbone Organization of Polymer Semiconductors through Semifluoroalkyl Side Chains.

While high-mobility p-type conjugated polymers have been widely reported, high-mobility n-type conjugated polymers are still rare. In the present work, we designed semifluorinated alkyl side chains and introduced them into naphthalene diimide-based polymers (PNDIF-T2 and PNDIF-TVT). We found that the strong self-organization of these side chains induced a high degree of order in the attached polymer backbones by forming a superstructure composed of "backbone crystals" and "side-chain crystals". This phenomenon was shown to greatly enhance the ordering along the backbone direction, and the resulting polymers thus exhibited unipolar n-channel transport in field-effect transistors with remarkably high electron mobility values of up to 6.50 cm(2) V(-1) s(-1) and with a high on-off current ratio of 10(5).