Highly Stretchable Stress-Strain Sensor from Elastomer Nanocomposites with Movable Cross-links and Ketjenblack.

Practical applications like very thin stress-strain sensors require high strength, stretchability, and conductivity, simultaneously. One of the approaches is improving the toughness of the stress-strain sensing materials. Polymeric materials with movable cross-links in which the polymer chain penetrates the cavity of cyclodextrin (CD) demonstrate enhanced strength and stretchability, simultaneously. We designed two approaches that utilize elastomer nanocomposites with movable cross-links and carbon filler (ketjenblack, KB). One approach is mixing SC (a single movable cross-network material), a linear polymer (poly(ethyl acrylate), PEA), and KB to obtain their composite. The electrical resistance increases proportionally with tensile strain, leading to the application of this composite as a stress-strain sensor. The responses of this material are stable for over 100 loading and unloading cycles. The other approach is a composite made with KB and a movable cross-network elastomer for knitting dissimilar polymers (KP), where movable cross-links connect the CD-modified polystyrene (PSCD) and PEA. The obtained composite acts as a highly sensitive stress-strain sensor that exhibits an exponential increase in resistance with increasing tensile strain due to the polymer dethreading from the CD rings. The designed preparations of highly repeatable or highly responsive stress-strain sensors with good mechanical properties can help broaden their application in electrical devices.

Synergic effect of graphene oxide and boron nitride on the mechanical properties of polyimide composite films.

The addition of two-dimensional (2D) materials into polymers can improve their mechanical properties. In particular, graphene oxide (GO) and hexagonal boron nitride (h-BN) are expected to be potential nanoplatelet additives for polymers. Interactions between such nanoplatelets and polymers are effective in improving the above properties. However, no report has investigated the effect of using two types of nanoplatelets that have good interaction with polymers. In this study, we fabricated polyimide (PI) films that contain two types of nanoplatelets, amine-functionalized h-BN (BNNH2 ) and GO. We have elucidated that the critical ratio and the content of BNNH2 and GO within PI govern the films' mechanical properties. When the BNNH2 /GO weight ratio was 52 : 1 and their content was 1 wt% in the PI film, the tensile modulus and tensile strength were increased by 155.2 MPa and 4.2 GPa compared with the pristine PI film.

Tunable Chemical Coupling in Two-Dimensional van der Waals Electrostatic Heterostructures.

Heterostructures of two-dimensional (2D) atomic crystals provide fascinating molecular-scale design elements for emergent physical phenomena and functional materials, as integrating distinct monolayers into vertical heterostructures can afford coupling between disparate properties. However, the available examples have been limited to either van der Waals (vdW) or electrostatic (ES) heterostructures that are solely composed of noncharged and charged monolayers, respectively. Here, we propose a "vdW-ES heterostructure" chemical design in which charge-neutral and charged monolayer-building blocks with highly disparate chemical and physical properties are conjugated vertically through asymmetrically charged interfaces. We demonstrate vdW-ES heteroassembly of semiconducting MoS2 and dielectric Ca2Nb3O10- (CNO) monolayers using an amphipathic molecular starch, resulting in the emergence of trion luminescence observed at the lowest energy among MoS2-related materials, probably due to interfacial confinement effects given by vdW-ES dual interactions. In addition, interface engineering leads to tailored exciton of the vdW/ES heterostructures owing to the pronounced dielectric proximity effects, bringing an intriguing interlayer chemistry to modify 2D materials. Furthermore, the current approach was successfully extended to create a graphene/CNO heterostructure, which verifies the versatility of the preparative method.

Work Function Lowering of Graphite by Sequential Surface Modifications: Nitrogen and Hydrogen Plasma Treatment.

Graphite-related materials play an important role in various kinds of devices and catalysts. Controlling the properties of such materials is of great significance to widen the potential applications and improve the performance of such applications as field emission devices and catalyst for fuel cells. In particular, the work function strongly affects the performance, and thus development of methods to tune the work function widely is urgently required. Here, we achieved wide-range control of the work function of graphite by nitrogen and hydrogen plasma treatments. The time of hydrogen plasma treatment and the amount of nitrogen atoms doped beforehand could control the work function of graphite from 2.9 to 5.0 eV. The formation of a surface dipole layer and the nitrogen-derived electron donation contributed to such lowering of the work function, which is advantageous for applications in various fields.

High degree reduction and restoration of graphene oxide on SiO2 at low temperature via remote Cu-assisted plasma treatment.

A high throughput synthesis method of graphene has been required for a long time to apply graphene to industrial applications. Of the various synthesis methods, the chemical exfoliation of graphite via graphene oxide (GO) is advantageous as far as productivity is concerned; however, the quality of the graphene produced by this method is far inferior to that synthesized by other methods, such as chemical vapor deposition on metals. Developing an effective reduction and restoration method for GO on dielectric substrates has been therefore a key issue. Here, we present a method for changing GO deposited on a dielectric substrate into high crystallinity graphene at 550 °C; this method uses CH4/H2 plasma and a Cu catalyst. We found that Cu remotely catalyzed the high degree reduction and restoration of GO on SiO2 and the effect ranged over at least 8 mm. With this method, field-effect transistor devices can be fabricated without any post treatment such as a transfer process. This plasma treatment increased electron and hole mobilities of GO to 480 cm2 V-1 s-1 and 460 cm2 V-1 s-1 respectively; these values were more than 50 times greater than that of conventional reduced GO. Furthermore, the on-site conversion ensured that the shape of the GO sheets remained unchanged after the treatment. This plasma treatment realizes the high throughput synthesis of a desired shaped graphene on any substrate without any residue and damage being caused by the transfer process; as such, it expands the potential applicability of graphene.

Growth temperature dependence of nitrogen doped graphene structure on Pt (111) and analysis of its reactivity with oxygen.

Nitrogen doping is an effective method for modulating the electronic states and properties of graphene. In particular, chemical vapor deposition using nitrogen-containing organic molecules such as pyridine has been expected to be a facile way to control the doping site and amount of nitrogen. However, the atomic structure of nitrogen-doped graphene (NG) synthesized from such molecules has not been investigated. Furthermore, the nitrogen doping sites of NG synthesized at a high temperature of more than 1000 K have also not been measured. In this study, we carried out Scanning Tunneling Microscopy (STM) measurements on the structure of NG synthesized from pyridine, and elucidated the doping sites. Furthermore, we investigated how the doping of nitrogen atoms affects the reactivity with oxygen molecules to reveal the active site of a carbon alloy catalyst. We found that NG synthesized at 1150 K has nitrogen atoms doped into the pyridinic site, and these pyridinic sites enhance the reactivity to oxygen when comparing the defects with/without nitrogen. These findings will help with the synthesis of NG when controlling the doping sites and the development of a catalyst with high efficiency.

Self-Aligned Growth of Organic Semiconductor Single Crystals by Electric Field.

We proposed a novel but facile method for growing organic semiconductor single-crystals via solvent vapor annealing (SVA) under electric field. In the conventional SVA growth process, nuclei of crystals appeared anywhere on the substrate and their crystallographic axes were randomly distributed. We applied electric field during the SVA growth of 2,7-dioctyl[1]benzothieno[3,2-b][1]benzothiophene (C8-BTBT) on the SiO2/Si substrate on which a pair of electrodes had been deposited beforehand. Real-time observation of the SVA process revealed that rodlike single crystals grew with their long axes parallel to the electric field and bridged the prepatterned electrodes. As a result, C8-BTBT crystals automatically formed a field effect transistor (FET) structure and the mobility reached 1.9 cm(2)/(V s). Electric-field-assisted SVA proved a promising method for constructing high-mobility single-crystal FETs at the desired position by a low-cost solution process.

The influence of source molecule structure on the low temperature growth of nitrogen-doped graphene.

Doping of heteroatoms such as nitrogen into the lattice structure of graphene can tune and tailor the overall electronic properties. N-doped graphene, depending on the nitrogen bonding mode and/or bonding configuration, displays subtly altered properties in comparison to pristine graphene. However, there remains a disappointing shortage of reliable methods for introducing dopants in a controlled and reproducible manner, preventing a thorough understanding of the relationship between structure and properties. In this study we aimed to prepare graphenes with nitrogen atoms doped at a graphitic (quaternary) site by depositing a source molecule containing a graphitic nitrogen atom: 4,4,8,8,12,12-hexamethyl-8,12-dihydro-4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine or 4H-benzo[9,1]quinolizino[3,4,5,6,7-defg]acridine-4,8,12-trione, on a heated Pt(111) substrate. At 400 °C, graphene with nitrogen atoms exclusively doped at a graphitic site was synthesized from the former molecule, while not from the latter molecule at any temperature. The present result indicates that the rational design of a source molecule is quite important for controlling the nitrogen doped site in the graphene lattice.

Electric-field-assisted position and orientation control of organic single crystals.

We have investigated the motion of growing pentacene single crystals in solution under various electric fields. The pentacene single crystals in 1,2,4-trichlorobenzene responded to the electric field as if they were positively charged. By optimizing the strength and frequency of an alternating electric field, the pentacene crystals automatically bridged the electrodes on SiO2. The pentacene crystal with a large aspect ratio tended to direct the [1̅10] orientation parallel to the conduction direction, which will be suitable from a viewpoint of anisotropy in mobility. The present result shows a possibility of controlling the position and orientation of organic single crystals by the use of an electric field, which leads to high throughput and low cost industrial manufacturing of the single crystal array from solution.