Effect of Molecular Stacking on Exciton Diffusion in Crystalline Organic Semiconductors.

Exciton diffusion is at the heart of most organic optoelectronic devices' operation, and it is currently the most limiting factor to their achieving high efficiency. It is deeply related to molecular organization, as it depends on intermolecular distances and orbital overlap. However, there is no clear guideline for how to improve exciton diffusion with regard to molecular design and structure. Here, we use single-crystal charge-transfer interfaces to probe favorable exciton diffusion. Photoresponse measurements on interfaces between perylenediimides and rubrene show a higher photocurrent yield (+50%) and extended spectral coverage (+100 nm) when there is increased dimensionality of the percolation network and stronger orbital overlap. This is achieved by very short interstack distances in different directional axes, which favors exciton diffusion by a Dexter mechanism. Even if the core of the molecule shows strong deviation from planarity, the similar electrical resistance of the different systems, planar and nonplanar, shows that electronic transport is not compromised. These results highlight the impact of molecular organization in device performance and the necessity of optimizing it to take full advantage of the materials' properties.

(α-DT-TTF)2[Au(mnt)2]: a weakly disordered molecular spin-ladder system.

The synthesis and characterization of (α-DT-TTF)2[Au(mnt)2] is reported. The magnetic properties of this new salt show that it is still a rare example of an organic spin-ladder. (α-DT-TTF)2[Au(mnt)2] shares the same ladder structure of the DT-TTF and ETT-TTF analogues, and its room temperature conductivity is ∼2 S/cm. Despite the observed donor orientation disorder associated with the thiophenic sulfur atoms, the intermolecular interactions between donor units, calculated using the extended Hückel approximation and a double-ξ basis set, show that the interaction values do not depend on the configuration of the sulfur atom on the thiophenic ring. The insensitivity of the spin-ladder magnetic properties to the donor molecular disorder in (α-DT-TTF)2[Au(mnt)2] is a direct consequence of the negligible contribution of the disordered thiophenic sulfur atom to the HOMO. In the related donor ETT-TTF, this contribution is significant and destroys the magnetic interactions, and no spin-ladder is observed. This compound not only enlarges the number of organic spin-ladder systems in this series of closely related compounds but also provides an interesting example of weakly disordered molecular spin-ladder system.

Piezoelectric Property of Electrospun PVDF Nanofibers as Linking Tips of Artificial-Hair-Cell Structures in Cochlea.

The death of hair cells and damage of natural tip links is one of the main causes of hearing-loss disability, and the development of an advanced artificial hearing aid holds the key to assisting those suffering from hearing loss. This study demonstrates the potential of using electrospun polyvinylidene fluoride (PVDF) fibers to serve as the artificial tip links, for long-term hearing-aid-device development based on their piezoelectric properties. We have shown that the electrospun PVDF-fiber web, consisting of fibers ranging from 30-220 nm in diameter with high ß-phase content, possesses the high piezoresponse of 170 mV. Analyses based on combined characterization methods including SEM, TEM, XRD, FTIR, Raman, DSC, XPS, PFM and piezoelectricity have confirmed that an optimized value of 15 wt.% PVDF could act as an effective candidate for a tip-link connector in a vibration-frequency prototype. Based on this easily reproducible electrospinning technique and the multifunctionalities of the resulting PVDF fibers, this fundamental study may shed light on the bio-inspired design of artificial, self-powered, high performance, hair-cell-like sensors in cochlea to tackle the hearing loss issue.

Low Operating Voltage Carbon-Graphene Hybrid E-textile for Temperature Sensing.

Graphene-coated polypropylene (PP) textile fibers are presented for their use as temperature sensors. These temperature sensors show a negative thermal coefficient of resistance (TCR) in a range between 30 and 45 °C with good sensitivity and reliability and can operate at voltages as low as 1 V. The analysis of the transient response of the temperature on resistance of different types of graphene produced by chemical vapor deposition (CVD) and shear exfoliation of graphite (SEG) shows that trilayer graphene (TLG) grown on copper by CVD displays better sensitivity due to the better thickness uniformity of the film and that carbon paste provides good contact for the measurements. Along with high sensitivity, TLG on PP shows not only the best response but also better transparency, mechanical stability, and washability compared to SEG. Temperature-dependent Raman analysis reveals that the temperature has no significant effect on the peak frequency of PP and expected effect on graphene in the demonstrated temperature range. The presented results demonstrate that these flexible, lightweight temperature sensors based on TLG with a negative TCR can be easily integrated in fabrics.

Water-Based Solution Processing and Wafer-Scale Integration of All-Graphene Humidity Sensors.

One of the main advantages of 2D materials for various applications is that they can be prepared in form of water-based solutions. The high yield and cost-effectiveness of this method make them of great interest for printed electronics, composites, and bio- and healthcare technologies. However, once deposited on a substrate, etching away these solution-processed materials is a difficult task, yet crucial for pattern definition and thus device fabrication. In particular, the realization of micrometer-sized patterns requires mesh and paste optimization when screen-printed or solvent-engineered and surface functionalization when inkjet-printed, both usually involving additional postdeposition steps. These constraints are holding back the integration of these 2D materials in devices and applications. In this work, a method for the fabrication of micrometer-sized well-defined patterns in water-based 2D materials is presented, with an extensive characterization of the films and patterns obtained. The method is ultimately used to create humidity sensors with performance comparable to that of commercial ones. These sensor devices are fabricated onto a 4' silicon and polyethylene terephthalate (PET) wafers to create all-graphene humidity sensors that are flexible, transparent, and compatible with current complementary metal-oxide-semiconductor (CMOS) and roll-to-roll workflows.

A New Facile Route to Flexible and Semi-Transparent Electrodes Based on Water Exfoliated Graphene and their Single-Electrode Triboelectric Nanogenerator.

Wearable technologies are driving current research efforts to self-powered electronics, for which novel high-performance materials such as graphene and low-cost fabrication processes are highly sought.The integration of high-quality graphene films obtained from scalable water processing approaches in emerging applications for flexible and wearable electronics is demonstrated. A novel method for the assembly of shear exfoliated graphene in water, comprising a direct transfer process assisted by evaporation of isopropyl alcohol is developed. It is shown that graphene films can be easily transferred to any target substrate such as paper, flexible polymeric sheets and fibers, glass, and Si substrates. By combining graphene as the electrode and poly(dimethylsiloxane) as the active layer, a flexible and semi-transparent triboelectric nanogenerator (TENG) is demonstrated for harvesting energy. The results constitute a new step toward the realization of energy harvesting devices that could be integrated with a wide range of wearable and flexible technologies, and opens new possibilities for the use of TENGs in many applications such as electronic skin and wearable electronics.

Towards conductive textiles: coating polymeric fibres with graphene.

Conducting fibres are essential to the development of e-textiles. We demonstrate a method to make common insulating textile fibres conductive, by coating them with graphene. The resulting fibres display sheet resistance values as low as 600 Ωsq-1, demonstrating that the high conductivity of graphene is not lost when transferred to textile fibres. An extensive microscopic study of the surface of graphene-coated fibres is presented. We show that this method can be employed to textile fibres of different materials, sizes and shapes, and to different types of graphene. These graphene-based conductive fibres can be used as a platform to build integrated electronic devices directly in textiles.