On-device phase engineering.

In situ tailoring of two-dimensional materials' phases under external stimulus facilitates the manipulation of their properties for electronic, quantum and energy applications. However, current methods are mainly limited to the transitions among phases with unchanged chemical stoichiometry. Here we propose on-device phase engineering that allows us to realize various lattice phases with distinct chemical stoichiometries. Using palladium and selenide as a model system, we show that a PdSe2 channel with prepatterned Pd electrodes can be transformed into Pd17Se15 and Pd4Se by thermally tailoring the chemical composition ratio of the channel. Different phase configurations can be obtained by precisely controlling the thickness and spacing of the electrodes. The device can be thus engineered to implement versatile functions in situ, such as exhibiting superconducting behaviour and achieving ultralow-contact resistance, as well as customizing the synthesis of electrocatalysts. The proposed on-device phase engineering approach exhibits a universal mechanism and can be expanded to 29 element combinations between a metal and chalcogen. Our work highlights on-device phase engineering as a promising research approach through which to exploit fundamental properties as well as their applications.

Organometallic Compound Stabilizes All-Inorganic Tin-Based Perovskite Nanocrystals Against Antisolvent Post-Treatment.

The isolation and purification of all-inorganic Sn-based perovskite nanocrystals (PNCs) remain troublesome, as common antisolvents accelerate the collapse of the optically active perovskite structure. Here, we mitigate such instabilities and endow strong resistance to antisolvent by incorporating the organometallic compound zinc diethyldithiocarbamate, Zn(DDTC)2, during the solution-based synthesis of all-inorganic CsSnI3 nanocrystals. Thiourea is shown to form through the thermal-driven conversion of Zn(DDTC)2 during synthesis, which binds to un-passivated Sn sites on the crystal surface and shields it from irreversible oxidation reactions. The CsSnI3 PNCs capped with thiourea show great stability after two purification cycles using methyl acetate, with negligible change in morphology, phase, and optical properties. Moreover, the modified PNCs are resistant to other commonly used antisolvents, like ethyl acetate, 1-pentanol, and isopropanol, offering a platform to explore all-inorganic Sn-based nanocrystalline thin films and optoelectronics.

Constrained patterning of orientated metal chalcogenide nanowires and their growth mechanism.

One-dimensional metallic transition-metal chalcogenide nanowires (TMC-NWs) hold promise for interconnecting devices built on two-dimensional (2D) transition-metal dichalcogenides, but only isotropic growth has so far been demonstrated. Here we show the direct patterning of highly oriented Mo6Te6 NWs in 2D molybdenum ditelluride (MoTe2) using graphite as confined encapsulation layers under external stimuli. The atomic structural transition is studied through in-situ electrical biasing the fabricated heterostructure in a scanning transmission electron microscope. Atomic resolution high-angle annular dark-field STEM images reveal that the conversion of Mo6Te6 NWs from MoTe2 occurs only along specific directions. Combined with first-principles calculations, we attribute the oriented growth to the local Joule-heating induced by electrical bias near the interface of the graphite-MoTe2 heterostructure and the confinement effect generated by graphite. Using the same strategy, we fabricate oriented NWs confined in graphite as lateral contact electrodes in the 2H-MoTe2 FET, achieving a low Schottky barrier of 11.5 meV, and low contact resistance of 43.7 Ω µm at the metal-NW interface. Our work introduces possible approaches to fabricate oriented NWs for interconnections in flexible 2D nanoelectronics through direct metal phase patterning.

General Synthesis of 2D Magnetic Transition Metal Dihalides via Trihalide Reduction.

Two-dimensional (2D) transition metal dihalides (TMDHs) have been receiving extensive attention due to their diversified magnetic properties and promising applications in spintronics. However, controlled growth of 2D TMDHs remains challenging owing to their extreme sensitivity to atmospheric moisture. Herein, using a home-built nitrogen-filled interconnected glovebox system, a universal chemical vapor deposition synthesis route of high-quality 2D TMDH flakes (1T-FeCl2, FeBr2, VCl2, and VBr2) by reduction of their trihalide counterparts is developed. Representatively, ultrathin (∼8.6 nm) FeCl2 flakes are synthesized on SiO2/Si, while on graphene/Cu foil the thickness can be down to monolayer (1L). Reflective magnetic circular dichroism spectroscopy shows an interlayer antiferromagnetic ordering of FeCl2 with a Neel temperature at ∼17 K. Scanning tunneling microscopy and spectroscopy further identify the atomic-scale structures and band features of 1L and bilayer FeCl2 on graphene/Cu foil.

Engineering the Crack Structure and Fracture Behavior in Monolayer MoS2 By Selective Creation of Point Defects.

Monolayer transition-metal dichalcogenides, e.g., MoS2 , typically have high intrinsic strength and Young's modulus, but low fracture toughness. Under high stress, brittle fracture occurs followed by cleavage along a preferential lattice direction, leading to catastrophic failure. Defects have been reported to modulate the fracture behavior, but pertinent atomic mechanism still remains elusive. Here, sulfur (S) and MoSn point defects are selectively created in monolayer MoS2 using helium- and gallium-ion-beam lithography, both of which reduce the stiffness of the monolayer, but enhance its fracture toughness. By monitoring the atomic structure of the cracks before and after the loading fracture, distinct atomic structures of the cracks and fracture behaviors are found in the two types of defect-containing monolayer MoS2 . Combined with molecular dynamics simulations, the key role of individual S and MoSn point defects is identified in the fracture process and the origin of the enhanced fracture toughness is elucidated. It is a synergistic effect of defect-induced deflection and bifurcation of cracks that enhance the energy release rate, and the formation of widen crack tip when fusing with point defects that prevents the crack propagation. The findings of this study provide insights into defect engineering and flexible device applications of monolayer MoS2 .

Tuning of Optical Behavior in Monolayer and Bilayer Molybdenum Disulfide Using Hydrostatic Pressure.

Researchers have shown great interest in two-dimensional crystals recently, because of their thickness-dependent electronic and optical properties. We have investigated the Raman and photoluminescence spectra of free-standing monolayer and bilayer MoS2, as a function of pressure. As the enforcement of layer interaction, an electronic and a crystal phase transition were revealed at ∼6 GPa and ∼16 GPa, respectively, in bilayer MoS2, while no phase transition in the monolayer is observed. The electronic phase transition at ∼6 GPa is supposed to be a direct interband changing to an indirect Λ-K interband transition, and the new structure shown at ∼16 GPa is not metallized and supposed to be a transformation from stacking faults due to layer sliding like 2Hc to 2Ha. The different pressure-induced features of monolayer MoS2, compared with bilayer MoS2, can help to get a better understanding about the importance of interlayer interaction on modifying the optical properties of MoS2 and other fundamental understanding of 2D materials.

The confinement effect of layered double hydroxides on intercalated pyromellitic acidic anions and highly selective uranium extraction from simulated seawater.

Oxygen-rich pyromellitic acidic anions (PMA4-) have been intercalated into MgAl-layered double hydroxides to fabricate the MgAl-PMA-LDH (abbr. PMA-LDH) composite exhibiting excellent adsorption performance toward uranium (U(VI)). Benefiting from the large number of functional groups of -COO-, the PMA-LDH displays an extremely large maximum U adsorption capacity (qUm) of 352 mg g-1 and an ultra-fast sorption rate, reaching uptakes of ∼97% within 30 min and >99% in 1 h at the initial U concentration (CU0) of 113 ppm. Over a very wide pH range of 5-11, high U removals (>93%) are achieved at CU0 = 105 ppm. Moreover, in the presence of highly concentrated competitive ions, ultra-high selectivity of UO22+ is observed, giving a very large distribution coefficient (Kd) of ∼106 mL g-1. Moreover, the PMA-LDH exhibits effective capture of UO22+ in contaminated simulated seawater, showing high uptakes of >93% at CU0 ∼ 10 ppm and >98% at CU0 ∼ 100 ppm. The dispersion effect of LDH layers may contribute to the increase of U adsorption capacity, and the confinement effect of LDH is conducive to the improvement of sorption selectivity toward U. The exploration of the interaction mechanism of UO22+ with PMA4- confined within the LDH gallery offers an important basis for the fabrication of new kinds of organic/inorganic hybrid materials. The PMA-LDH is a highly effective adsorbent which can be applied to uranium extraction from seawater and uranium disposal in nuclear wastewater.

Continuously tunable ferroelectric domain width down to the single-atomic limit in bismuth tellurite.

Emerging functionalities in two-dimensional materials, such as ferromagnetism, superconductivity and ferroelectricity, open new avenues for promising nanoelectronic applications. Here, we report the discovery of intrinsic in-plane room-temperature ferroelectricity in two-dimensional Bi2TeO5 grown by chemical vapor deposition, where spontaneous polarization originates from Bi column displacements. We found an intercalated buffer layer consist of mixed Bi/Te column as 180° domain wall which enables facile polarized domain engineering, including continuously tunable domain width by pinning different concentration of buffer layers, and even ferroelectric-antiferroelectric phase transition when the polarization unit is pinned down to single atomic column. More interestingly, the intercalated Bi/Te buffer layer can interconvert to polarized Bi columns which end up with series terraced domain walls and unusual fan-shaped ferroelectric domain. The buffer layer induced size and shape tunable ferroelectric domain in two-dimensional Bi2TeO5 offer insights into the manipulation of functionalities in van der Waals materials for future nanoelectronics.

Dative Epitaxy of Commensurate Monocrystalline Covalent van der Waals Moiré Supercrystal.

Realizing van der Waals (vdW) epitaxy in the 1980s represents a breakthrough that circumvents the stringent lattice matching and processing compatibility requirements in conventional covalent heteroepitaxy. However, due to the weak vdW interactions, there is little control over film qualities by the substrate. Typically, discrete domains with a spread of misorientation angles are formed, limiting the applicability of vdW epitaxy. Here, the epitaxial growth of monocrystalline, covalent Cr5 Te8 2D crystals on monolayer vdW WSe2 by chemical vapor deposition is reported, driven by interfacial dative bond formation. The lattice of Cr5 Te8 , with a lateral dimension of a few tens of micrometers, is fully commensurate with that of WSe2 via 3 × 3 (Cr5 Te8 )/7 × 7 (WSe2 ) supercell matching, forming a single-crystalline moiré superlattice. This work establishes a conceptually distinct paradigm of thin-film epitaxy, termed "dative epitaxy", which takes full advantage of covalent epitaxy with chemical bonding for fixing the atomic registry and crystal orientation, while circumventing its stringent lattice matching and processing compatibility requirements; conversely, it ensures the full flexibility of vdW epitaxy, while avoiding its poor orientation control. Cr5 Te8 2D crystals grown by dative epitaxy exhibit square magnetic hysteresis, suggesting minimized interfacial defects that can serve as pinning sites.