Thermodynamically Driven Tilt Grain Boundaries of Monolayer Crystals Using Catalytic Liquid Alloys.

We report a method to precisely control the atomic defects at grain boundaries (GBs) of monolayer MoS2 by vapor-liquid-solid (VLS) growth using sodium molybdate liquid alloys, which serve as growth catalysts to guide the formations of the thermodynamically most stable GB structure. The Mo-rich chemical environment of the alloys results in Mo-polar 5|7 defects with a yield exceeding 95%. The photoluminescence (PL) intensity of VLS-grown polycrystalline MoS2 films markedly exceeds that of the films, exhibiting abundant S 5|7 defects, which are kinetically driven by vapor-solid-solid growths. Density functional theory calculations indicate that the enhanced PL intensity is due to the suppression of nonradiative recombination of charged excitons with donor-type defects of adsorbed Na elements on S 5|7 defects. Catalytic liquid alloys can aid in determining a type of atomic defect even in various polycrystalline 2D films, which accordingly provides a technical clue to engineer their properties.

Wafer-Scale Programmed Assembly of One-Atom-Thick Crystals.

Crystalline films offer various physical properties based on the modulation of their thicknesses and atomic structures. The layer-by-layer assembly of atomically thin crystals provides a powerful means to arbitrarily design films at the atomic level, which are unattainable with existing growth technologies. However, atomically clean assembly of the materials with high scalability and reproducibility remains challenging. We report programmed crystal assembly of graphene and monolayer hexagonal boron nitride, assisted by van der Waals interactions, to form wafer-scale films of pristine interfaces with near-unity yield. The atomic configurations of the films are tailored with layer-resolved compositions and in-plane crystalline orientations. We demonstrate batch-fabricated tunnel device arrays with modulation of the resistance over orders of magnitude by thickness control of the hexagonal boron nitride barrier with single-atom precision and large-scale, twisted multilayer graphene with programmable electronic band structures and crystal symmetries. Our results constitute an important development in the artificial design of large-scale films.

Living Cationic Ring-Opening Polymerization of Hetero Diels-Alder Adducts to Give Multifactor-Controlled and Fast-Photodegradable Vinyl Polymers.

Precise control of multiple structural parameters associated with vinyl polymers is important for producing materials with the desired properties and functions. While the development of living polymerization methods has provided a way to control the various structural parameters of vinyl polymers, the concomitant control of their sequence and regioregularity remains a challenging task. To overcome this challenge, herein, we report the living cationic ring-opening polymerization of hetero Diels-Alder adducts. The scalable and modular synthesis of the cyclic monomers was achieved by a one-step protocol using readily available vinyl precursors. Subsequently, living polymerization of the cyclic monomers was examined, allowing the synthesis of vinyl polymers while controlling multiple factors, including molecular weight, dispersity, alternating sequence, head-to-head regioregularity, and end-group functionality. The living characteristics of the developed method were further demonstrated by block copolymerization. The synthesized vinyl polymers exhibited unique thermal properties and underwent fast photodegradation even under sunlight.

Femtosecond laser-assisted selective reduction of neovascularization in rat cornea.

Nonlinear multiphoton absorption induced by focusing near infrared (NIR) femtosecond (fs) laser pulses into a transparent cornea allows surgery on neovascular structures with minimal collateral damage. In this report, we introduce an fs laser-based microsurgery for selective treatment of rat corneal neovascularizations (in vivo). Contiguous tissue effects are achieved by scanning a focused laser pulse below the corneal surface with a fluence range of 2.2-8.6 J/cm(2). The minimal visible laser lesion (MVL) threshold determined over the corneal neovascular structures was found to be 4.3 J/cm(2). Histological and optical coherence tomography examinations of the anterior segment after laser irradiations show localized degeneration of neovascular structures without any unexpected change in adjacent tissues. Furthermore, an approximately 30 % reduction in corneal neovascularizations was observed after 5 days of fs laser exposure. The femtosecond laser is thus a promising tool for minimally invasive intrastromal surgery with the aid of a significantly smaller and more deterministic photodisruptive energy threshold for the interaction between the fs laser pulse and corneal neovascular structures.

Defect Passivation of 2D Semiconductors by Fixating Chemisorbed Oxygen Molecules via h-BN Encapsulations.

Hexagonal boron nitride (h-BN) is a key ingredient for various 2D van der Waals heterostructure devices, but the exact role of h-BN encapsulation in relation to the internal defects of 2D semiconductors remains unclear. Here, it is reported that h-BN encapsulation greatly removes the defect-related gap states by stabilizing the chemisorbed oxygen molecules onto the defects of monolayer WS2 crystals. Electron energy loss spectroscopy (EELS) combined with theoretical analysis clearly confirms that the oxygen molecules are chemisorbed onto the defects of WS2 crystals and are fixated by h-BN encapsulation, with excluding a possibility of oxygen molecules trapped in bubbles or wrinkles formed at the interface between WS2 and h-BN. Optical spectroscopic studies show that h-BN encapsulation prevents the desorption of oxygen molecules over various excitation and ambient conditions, resulting in a greatly lowered and stabilized free electron density in monolayer WS2 crystals. This suppresses the exciton annihilation processes by two orders of magnitude compared to that of bare WS2. Furthermore, the valley polarization becomes robust against the various excitation and ambient conditions in the h-BN encapsulated WS2 crystals.

Engineering Grain Boundaries in Two-Dimensional Electronic Materials.

Engineering the boundary structures in 2D materials provides an unprecedented opportunity to program the physical properties of the materials with extensive tunability and realize innovative devices with advanced functionalities. However, structural engineering technology is still in its infancy, and creating artificial boundary structures with high reproducibility remains difficult. In this review, various emergent properties of 2D materials with different grain boundaries, and the current techniques to control the structures, are introduced. The remaining challenges for scalable and reproducible structure control and the outlook on the future directions of the related techniques are also discussed.

High-Performance Solution-Processed 2D P-Type WSe2 Transistors and Circuits through Molecular Doping.

Semiconducting ink based on 2D single-crystal flakes with dangling-bond-free surfaces enables the implementation of high-performance devices on form-free substrates by cost-effective and scalable printing processes. However, the lack of solution-processed p-type 2D semiconducting inks with high mobility is an obstacle to the development of complementary integrated circuits. Here, a versatile strategy of doping with Br2 is reported to enhance the hole mobility by orders of magnitude for p-type transistors with 2D layered materials. Br2 -doped WSe2 transistors show a field-effect hole mobility of more than 27 cm2  V-1  s-1 , and a high on/off current ratio of ≈107 , and exhibits excellent operational stability during the on-off switching, cycling, and bias stressing testing. Moreover, complementary inverters composed of patterned p-type WSe2 and n-type MoS2 layered films are demonstrated with an ultra-high gain of 1280 under a driving voltage (VDD ) of 7 V. This work unveils the high potential of solution-processed 2D semiconductors with low-temperature processability for flexible devices and monolithic circuitry.

Electrochemical C(sp3)-H Functionalization of γ-Lactams Based on Hydrogen Atom Transfer.

We describe the electrochemical α-amidoalkylation of γ-lactams based on transition-metal-free cross-coupling via hydrogen atom transfer. The highly selective hydrogen atom transfer process allows for a broad substrate scope including both inter- and intramolecular reactions. Also, the construction of quaternary centers was realized by a double hydrogen atom transfer protocol to afford spirocycles. Detailed mechanistic studies including experimental and computational studies are provided to support the reaction pathway.

Large Memory Window of van der Waals Heterostructure Devices Based on MOCVD-Grown 2D Layered Ge4 Se9.

Van der Waals (vdW) heterostructures have drawn much interest over the last decade owing to their absence of dangling bonds and their intriguing low-dimensional properties. The emergence of 2D materials has enabled the achievement of significant progress in both the discovery of physical phenomena and the realization of superior devices. In this work, the group IV metal chalcogenide 2D-layered Ge4 Se9 is introduced as a new selection of insulating vdW material. 2D-layered Ge4 Se9 is synthesized with a rectangular shape using the metalcorganic chemical vapor deposition system using a liquid germanium precursor at 240 °C. By stacking the Ge4 Se9 and MoS2 , vdW heterostructure devices are fabricated with a giant memory window of 129 V by sweeping back gate range of ±80 V. The gate-independent decay time reveals that the large hysteresis is induced by the interfacial charge transfer, which originates from the low band offset. Moreover, repeatable conductance changes are observed over the 2250 pulses with low non-linearity values of 0.26 and 0.95 for potentiation and depression curves, respectively. The energy consumption of the MoS2 /Ge4 Se9 device is about 15 fJ for operating energy and the learning accuracy of image classification reaches 88.3%, which further proves the great potential of artificial synapses.

Effects of Lightning on the Magnetic Properties of Volcanic Ash.

High-current impulse experiments were performed on volcanic ash samples to determine the magnetic effects that may result from the occurrence of volcanic lightning during explosive eruptions. Pseudo-ash was manufactured through milling and sieving of eruptive deposits with different bulk compositions and mineral contents. By comparing pre- and post-experimental samples, it was found that the saturation (i.e., maximum possible) magnetization increased, and coercivity (i.e., ability to withstand demagnetization) decreased. The increase in saturation magnetization was greater for compositionally evolved samples compared to more primitive samples subjected to equivalent currents. Changes in remanent (i.e., residual) magnetization do not correlate with composition, and show wide variability. Variations in magnetic properties were generally more significant when samples were subjected to higher peak currents as higher currents affect a greater proportion of the subjected sample. The electrons introduced by the current impulse cause reduction and devolatilization of the ash grains, changing their structural, mineralogical, and magnetic properties.