Colloidal Synthesis of P-Type Zn3As2 Nanocrystals.

Zinc pnictides, particularly Zn3As2, hold significant promise for optoelectronic applications owing to their intrinsic p-type behavior and appropriate bandgaps. However, despite the outstanding properties of colloidal Zn3As2 nanocrystals, research in this area is lacking because of the absence of suitable precursors, occurrence of surface oxidation, and intricacy of the crystal structures. In this study, a novel and facile solution-based synthetic approach is presented for obtaining highly crystalline p-type Zn3As2 nanocrystals with accurate stoichiometry. By carefully controlling the feed ratio and reaction temperature, colloidal Zn3As2 nanocrystals are successfully obtained. Moreover, the mechanism underlying the conversion of As precursors in the initial phases of Zn3As2 synthesis is elucidated. Furthermore, these nanocrystals are employed as active layers in field-effect transistors that exhibit inherent p-type characteristics with native surface ligands. To enhance the charge transport properties, a dual passivation strategy is introduced via phase-transfer ligand exchange, leading to enhanced hole mobilities as high as 0.089 cm2 V-1 s-1. This study not only contributes to the advancement of nanocrystal synthesis, but also opens up new possibilities for previously underexplored p-type nanocrystal research.

Ligand-Crosslinking Strategy for Efficient Quantum Dot Light-Emitting Diodes via Thiol-Ene Click Chemistry.

While solution-processable colloidal quantum dots (QDs) offer cost-effective and large-scale manufacturing, they can be susceptible to subsequent solution processes, making continuous processing challenging. To enable complex and integrated device architectures, robust QD films with subsequent patterning are necessary. Here, we report a facile ligand-crosslinking strategy based on thiol-ene click chemistry. Thiol molecules added to QD films react with UV light to form radicals that crosslink with QD ligands containing carbon double bonds, enabling microscale photo-patterning of QD films and enhancing their solvent resistance. This strategy can also be extended to other ligand-capped nanocrystals. It is found that the swelling of QD films during the process of binding with the thiol molecules placed between the ligands contributes to the improvement of photoluminescence and electroluminescence properties. These results suggest that the thiol-ene crosslinking modifies the optoelectronic properties and enables direct optical patterning, expanding the potential applications of QDs.

Interfacial Force-Focusing Effect in Mechanophore-Linked Nanocomposites.

Enhanced force transmission to mechanophores is demonstrated in polymer nanocomposite materials. Spiropyran (SP) mechanophores that change color and fluorescence under mechanical stimuli are functionalized at the interface between SiO2 nanoparticles and polymers. Successful mechanical activation of SP at the interface is confirmed in both solution and solid states. Compared with SP-linked in bulk polymers, interfacial activation induces greater conversion of SP to its colored merocyanine form and also significantly decreases the activation threshold under tension. Experimental observations are supported by finite element simulation of the interfacial stress state. The interfacial force-focusing strategy opens a new way to control the reactivity of mechanophores and also potentially indicates interfacial damage in composite materials.

Regioisomer-Specific Mechanochromism of Naphthopyran in Polymeric Materials.

Transformation of naphthopyran into a colored merocyanine species in polymeric materials is achieved using mechanical force. We demonstrate that the mechanochemical reactivity of naphthopyran is critically dependent on the regiochemistry, with only one particular substitution pattern leading to successful mechanochemical activation. Two alternative regioisomers with different polymer attachment points are demonstrated to be mechanochemically inactive. This trend in reactivity is accurately predicted by DFT calculations, reinforcing predictive capabilities in mechanochemical systems. We rationalize the reactivity differences between naphthopyran regioisomers in terms of the alignment of the target C-O pyran bond with the direction of the applied mechanical force and its effect on mechanochemical transduction along the reaction coordinate.

Malleable and Recyclable Poly(urea-urethane) Thermosets bearing Hindered Urea Bonds.

Poly(urea-urethane) thermosets containing the 1-tert-butylethylurea (TBEU) structure feature a reversible dissociation/association process of their covalent linkages under mild conditions. Unlike conventional thermosets, TBEU-based poly(urea-urethane) thermosets maintain their malleability after curing. Under high temperature (100 °C) and applied pressure (300 kPa), ground TBEU thermoset powder can be remolded to bulk after 20 min.

Effect of Mechanical Stress on Spiropyran-Merocyanine Reaction Kinetics in a Thermoplastic Polymer.

Mechanical force alters the potential energy surface of a mechanophore reaction by modifying the activation energy for conversion. The effects of force on the rate constants and activation energies are not well characterized for mechanophores in bulk polymers. In this work, spiropyran-linked polyurethanes are synthesized and the kinetics of the spiropyran-merocyanine transition in the bulk polymer measured under different values of a macroscopic tensile stress. Above a critical threshold stress, the forward rate constant (spiropyran to merocyanine transition) increases, while the reverse rate constant (merocyanine to spiropyran transition) decreases with applied stress. A tensile stress of 50 MPa enhances the forward rate constant by 110% and lowers the forward activation energy by 1.8 kJ/mol compared to the unstressed condition. Also, this same amount of stress reduces the reverse rate constant by 65% and increases the reverse activation energy by 2.5 kJ/mol.

Floating compression of Ag nanowire networks for effective strain release of stretchable transparent electrodes.

Manipulation of the configuration of Ag nanowire (NW) networks has been pursued to enhance the performance of stretchable transparent electrodes. However, it has remained challenging due to the high Young's modulus and low yield strain of Ag NWs, which lead to their mechanical failure when subjected to structural deformation. We demonstrate that floating a Ag NW network on water and subsequent in-plane compression allows convenient development of a wavy configuration in the Ag NW network, which can release the applied strain. A greatly enhanced electromechanical stability of Ag NW networks can be achieved due to their wavy configuration, while the NW networks maintain the desirable optical and electrical properties. Moreover, the produced NW networks can be transferred to a variety of substrates, offering flexibility for device fabrication. The Ag NW networks with wavy configurations are used as compliant electrodes for dielectric elastomer actuators. The study demonstrates their promising potential to provide improved performance for soft electronic devices.

Engineering the shape and structure of materials by fractal cut.

In this paper we discuss the transformation of a sheet of material into a wide range of desired shapes and patterns by introducing a set of simple cuts in a multilevel hierarchy with different motifs. Each choice of hierarchical cut motif and cut level allows the material to expand into a unique structure with a unique set of properties. We can reverse-engineer the desired expanded geometries to find the requisite cut pattern to produce it without changing the physical properties of the initial material. The concept was experimentally realized and applied to create an electrode that expands to >800% the original area with only very minor stretching of the underlying material. The generality of our approach greatly expands the design space for materials so that they can be tuned for diverse applications.