Dynamics of Hydroxyl Anions Promotes Lithium Ion Conduction in Antiperovskite Li2OHCl.

Li2OHCl is an exemplar of the antiperovskite family of ionic conductors, for which high ionic conductivities have been reported, but in which the atomic-level mechanism of ion migration is unclear. The stable phase is both crystallographically defective and disordered, having ∼1/3 of the Li sites vacant, while the presence of the OH- anion introduces the possibility of rotational disorder that may be coupled to cation migration. Here, complementary experimental and computational methods are applied to understand the relationship between the crystal chemistry and ionic conductivity in Li2OHCl, which undergoes an orthorhombic to cubic phase transition near 311 K (≈38 °C) and coincides with the more than a factor of 10 change in ionic conductivity (from 1.2 × 10-5mS/cm at 37 °C to 1.4 × 10-3 mS/cm at 39 °C). X-ray and neutron experiments conducted over the temperature range 20-200 °C, including diffraction, quasi-elastic neutron scattering (QENS), the maximum entropy method (MEM) analysis, and ab initio molecular dynamics (AIMD) simulations, together show conclusively that the high lithium ion conductivity of cubic Li2OHCl is correlated to "paddlewheel" rotation of the dynamic OH- anion. The present results suggest that in antiperovskites and derivative structures a high cation vacancy concentration combined with the presence of disordered molecular anions can lead to high cation mobility.

Stretchable and Ambient Stable Perovskite/Polymer Luminous Hybrid Nanofibers of Multicolor Fiber Mats and Their White LED Applications.

We report the fabrication and optical/mechanical properties of perovskite/thermoplastic polyurethane (TPU)-based multicolor luminescent core-shell nanofibers and their large-scale fiber mats. One-step coaxial perovskite/TPU nanofibers had a high photoluminescence quantum yield value exceeding 23.3%, surpassing that of its uniaxial counterpart, due to the homogeneous distribution of perovskite nanoparticles (NPs) by the confinement of the TPU shell. The fabricated core-shell nanofibers exhibited a high mechanical endurance owing to the well elastic properties of TPU and maintained the luminescence intensity even under a 100% stretched state after 1000 stretching-relaxing cycles. By taking advantage of the hydrophobic nature of TPU, the ambient and moisture stability of the fabricated fibers were enhanced up to 1 month. Besides, large-area stretchable nanofibers with a dimension of 15 cm × 30 cm exhibiting various visible-light emission peaks were fabricated by changing the composition of perovskite NPs. Moreover, a large-scale luminescent and stretchable fiber mat was successfully fabricated by electrospinning. Furthermore, the white-light emission from the fabricated fibers and mats was achieved by incorporating orange-light-emitting poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] into the TPU shell and coupling the turquoise blue-light-emitting perovskite NPs in the core site. Finally, the integrity of the perovskite-based TPU fibers was realized by fabricating a light-emitting diode (LED) device containing the orange-light-emitting fibers embedded in the polyfluorene emissive layer. This work demonstrated an effective way to prepare stable and stretchable luminous nanofibers and the integration of such nanofibers into LED devices, which could facilitate the future development of wearable electronic devices.

Facile Preparation of Cu/Ag Core/Shell Electrospun Nanofibers as Highly Stable and Flexible Transparent Conductive Electrodes for Optoelectronic Devices.

Novel transparent conductive electrodes (TCEs) with copper (Cu)/silver (Ag) core/shell nanofibers (NFs) containing random, aligned, and crossed structures were prepared using a combination of electrospinning (ES) and chemical reduction. The ES process was used to prepare continuous copper nanofibers (Cu-NFs), which were used as core materials and were then immersed in silver ink (Ag ink) to form a protective layer of Ag to protect the Cu-NFs from oxidation. The Ag shell layer protected the Cu-NFs against oxidation and enhanced their conductivity. Such Cu/Ag core/shell webs can be easily transferred on the flexible matrix and can be applied in TCEs. The metal NF webs of different structures exhibited various degrees of conductivity and followed the order random type > crossed type > aligned type; however, the order with respect to transmittance ( T) was inverse. The aligned nanowire networks exhibited a high T of over 80%, and the random ones exhibited a low sheet resistance of less than 102 Ω/sq (the best value is 7.85 Ω/sq). The present study demonstrated that TCEs based on Cu/Ag core/shell NF webs have considerable flexibility, transparency, and conductivity and can be applied in novel flexible light-emitting diode devices and solar cells in the future.

Uniform Luminous Perovskite Nanofibers with Color-Tunability and Improved Stability Prepared by One-Step Core/Shell Electrospinning.

A one-step core/shell electrospinning technique is exploited to fabricate uniform luminous perovskite-based nanofibers, wherein the perovskite and the polymer are respectively employed in the core and the outer shell. Such a coaxial electrospinning technique enables the in situ formation of perovskite nanocrystals, exempting the needs of presynthesis of perovskite quantum dots or post-treatments. It is demonstrated that not only the luminous electrospun nanofibers can possess color-tunability by simply tuning the perovskite composition, but also the grain size of the formed perovskite nanocrystals is largely affected by the perovskite precursor stoichiometry and the polymer solution concentration. Consequently, the optimized perovskite electrospun nanofiber yields a high photoluminescence quantum yield of 30.9%, significantly surpassing the value of its thin-film counterpart. Moreover, owing to the hydrophobic characteristic of shell polymer, the prepared perovskite nanofiber is endowed with a high resistance to air and water. Its photoluminescence intensity remains constant while stored under ambient environment with a relative humidity of 85% over a month and retains intensity higher than 50% of its initial intensity while immersed in water for 48 h. More intriguingly, a white light-emitting perovskite-based nanofiber is successfully fabricated by pairing the orange light-emitting compositional perovskite with a blue light-emitting conjugated polymer.

Formation of alternating interfacial layers in Au-12Ge/Ni joints.

Au-Ge alloys are promising materials for high-power and high-frequency packaging, and Ni is frequently used as diffusion barriers. This study investigates interfacial reactions in Au-12Ge/Ni joints at 300 °C and 400 °C. For the reactions at 300 °C, typical interfacial morphology was observed and the diffusion path was (Au) + (Ge)/NiGe/Ni5Ge3/Ni. However, an interesting phenomenon--the formation of (Au,Ni,Ge)/NiGe alternating layers - was observed for the reactions at 400 °C. The diffusion path across the interface was liquid/(Au,Ni,Ge)/NiGe/· · ·/(Au,Ni,Ge)/NiGe/Ni2Ge/Ni. The periodic thermodynamic instability at the NiGe/Ni2Ge interface caused the subsequent nucleation of new (Au,Ni,Ge)/NiGe pairs. The thermodynamic foundation and mechanism of formation of the alternating layers are elaborated in this paper.