Direct observation of twisted stacking domains in the van der Waals magnet CrI3.

Van der Waals (vdW) stacking is a powerful technique to achieve desired properties in condensed matter systems through layer-by-layer crystal engineering. A remarkable example is the control over the twist angle between artificially-stacked vdW crystals, enabling the realization of unconventional phenomena in moiré structures ranging from superconductivity to strongly correlated magnetism. Here, we report the appearance of unusual 120° twisted faults in vdW magnet CrI3 crystals. In exfoliated samples, we observe vertical twisted domains with a thickness below 10 nm. The size and distribution of twisted domains strongly depend on the sample preparation methods, with as-synthesized unexfoliated samples showing tenfold thicker domains than exfoliated samples. Cooling induces changes in the relative populations among different twisting domains, rather than the previously assumed structural phase transition to the rhombohedral stacking. The stacking disorder induced by sample fabrication processes may explain the unresolved thickness-dependent magnetic coupling observed in CrI3.

An Ultra-Thin MXene Film for Multimodal Sensing of Neuroelectrical Signals with Artifacts Removal.

Neuroelectrical signals transmitted onto the skin tend to decay to an extremely weak level, making them highly susceptible to interference from the environment and body movement. Meanwhile, for comprehensively understanding cognitive nerve conduction, multimodal sensing of neural signals, such as magnetic resonance imaging (MRI) and functional near-infrared spectroscopy (fNIRS), is highly required. Previous metal or polymer conductors cannot either provide a seamless on-skin feature for accurate sensing of neuroelectrical signals or be compatible with multimodal imaging techniques without opto- and magnet- artifacts. Herein, a ≈20 nm thick MXene film that is able to simultaneously detect electrophysiological signals and perform imaging by MRI and fNIRS with high fidelity is reported. The ultrathin film is made of crosslinked Ti3 C2 Tx film via poly (3,4-ethylene dioxythiophene): polystyrene sulfonate (PEDOT: PSS), showing a record high electroconductivity and transparency combination (11 000 S cm-1 @89%). Among them, PEDOT: PSS not only plays a cross-linking role to stabilize MXene film but also shortens the interlayer distance for effective charge transfer and high transparency. Thus, it can achieve a low interfacial impedance with skin or neural surfaces for accurate recording of electrophysiological signals with low motion artifacts. Besides, the high transparency originating from the ultrathin feature leads to good compatibility with fNIRS and MRI without optical and magnetic artifacts, enabling multimodal cognitive neural monitoring during prolonged use.

Ultrafast van der Waals diode using graphene quantum capacitance and Fermi-level depinning.

Graphene, with superior electrical tunabilities, has arisen as a multifunctional insertion layer in vertically stacked devices. Although the role of graphene inserted in metal-semiconductor junctions has been well investigated in quasi-static charge transport regime, the implication of graphene insertion at ultrahigh frequencies has rarely been considered. Here, we demonstrate the diode operation of vertical Pt/n-MoSe2/graphene/Au assemblies at ~200-GHz cutoff frequency (fC). The electric charge modulation by the inserted graphene becomes essentially frozen above a few GHz frequencies due to graphene quantum capacitance-induced delay, so that the Ohmic graphene/MoSe2 junction may be transformed to a pinning-free Schottky junction. Our diodes exhibit much lower total capacitance than devices without graphene insertion, deriving an order of magnitude higher fC, which clearly demonstrates the merit of graphene at high frequencies.

Tailoring Two-Dimensional Matter Using Strong Light-Matter Interactions.

The shaping of matter into desired nanometric structures with on-demand functionalities can enhance the miniaturization of devices in nanotechnology. Herein, strong light-matter interaction was used as an optical lithographic tool to tailor two-dimensional (2D) matter into nanoscale architectures. We transformed 2D black phosphorus (BP) into ultrafine, well-defined, beyond-diffraction-limit nanostructures of ten times smaller size and a hundred times smaller spacing than the incident, femtosecond-pulsed light wavelength. Consequently, nanoribbons and nanocubes/cuboids scaling tens of nanometers were formed by the structured ablation along the extremely confined periodic light fields originating from modulation instability, the tailoring process of which was visualized in real time via light-coupled in situ transmission electron microscopy. The current findings on the controllable nanoscale shaping of BP will enable exotic physical phenomena and further advance the optical lithographic techniques for 2D materials.

5 nm Ultrathin Crystalline Ferroelectric P(VDF-TrFE)-Brush Tuned for Hysteresis-Free Sub 60 mV dec-1 Negative-Capacitance Transistors.

Negative-capacitance field-effect transistors (NC-FETs) have gathered enormous interest as a way to reduce subthreshold swing (SS) and overcome the issue of power dissipation in modern integrated circuits. For stable NC behavior at low operating voltages, the development of ultrathin ferroelectrics (FE), which are compatible with the industrial process, is of great interest. Here, a new scalable ultrathin ferroelectric polymer layer is developed based on trichloromethyl (CCl3 )-terminated poly(vinylidene difluoride-co-trifloroethylene) (P(VDF-TrFE)) to achieve the state-of-the-art performance of NC-FETs. The crystalline phase of 5-10 nm ultrathin P(VDF-TrFE) is prepared on AlOX by a newly developed brush method, which enables an FE/dielectric (DE) bilayer. FE/DE thickness ratios are then systematically tuned at ease to achieve ideal capacitance matching. NC-FETs with optimized FE/DE thickness at a thickness limit demonstrate hysteresis-free operation with an SS of 28 mV dec-1 at ≈1.5 V, which competes with the best reports. This P(VDF-TrFE)-brush layer can be broadly adapted to NC-FETs, opening an exciting avenue for low-power devices.

Negative Valley Polarization of the Intralayer Exciton via One-Step Growth of H-Type Heterobilayer WS2/MoS2.

Vertical type II van der Waals heterobilayers of transition metal dichalcogenides (TMDs) have attracted wide attention due to their distinctive features mostly arising from the emergence of intriguing electronic structures that include moiré-related phenomena. Owing to strong spin-orbit coupling under a noncentrosymmetric environment, TMD heterobilayers host nonequivalent +K and -K valleys of contrasting Berry curvatures, which can be optically controlled by the helicity of optical excitation. The corresponding valley selection rules are well established by not only intralayer excitons but also interlayer excitons. Quite intriguingly, here, we experimentally demonstrate that unusual valley switching can be achieved using the lowest-lying intralayer excitons in H-type heterobilayer WS2/MoS2 prepared by one-step growth. This TMD combination provides an ideal case for interlayer coupling with an almost perfect lattice match, thereby also in the momentum space between +K and -K valleys in the H-type heterostructure. The underlying valley-switching mechanism can be understood by bright-to-dark conversion of initially created electrons in the valley of WS2, followed by interlayer charge transfer to the opposite valley in MoS2. Our suggested model is also confirmed by the absence of valley switching when the lowest-lying excitons in MoS2 are directly generated in the heterobilayer. In contrast to the H-type case, we show that no valley switching is observed from R-type heterobilayers prepared by the same method, where interlayer charge transfer does not occur between the opposite valleys. We compare the case with the series of valley polarization data from other heterobilayer combinations obtained under different excitation energies and temperatures. Our valley switching mechanism can be utilized for valley manipulation by controlling the excitation photon energy together with the photon helicity in valleytronic devices derived from H-type TMD heterobilayers.

Unidirectional Alignment of AgCN Microwires on Distorted Transition Metal Dichalcogenide Crystals.

Van der Waals epitaxy on the surface of two-dimensional (2D) layered crystals has gained significant research interest for the assembly of well-ordered nanostructures and fabrication of vertical heterostructures based on 2D crystals. Although van der Waals epitaxial assembly on the hexagonal phase of transition metal dichalcogenides (TMDCs) has been relatively well characterized, a comparable study on the distorted octahedral phase (1T' or Td) of TMDCs is largely lacking. Here, we investigate the assembly behavior of one-dimensional (1D) AgCN microwires on various distorted TMDC crystals, namely 1T'-MoTe2, Td-WTe2, and 1T'-ReS2. The unidirectional alignment of AgCN chains is observed on these crystals, reflecting the symmetry of underlying distorted TMDCs. Polarized Raman spectroscopy and transmission electron microscopy directly confirm that AgCN chains display the remarkable alignment behavior along the distorted chain directions of underlying TMDCs. The observed unidirectional assembly behavior can be attributed to the favorable adsorption configurations of 1D chains along the substrate distortion, which is supported by our theoretical calculations and observation of similar assembly behavior from different cyanide chains. The aligned AgCN microwires can be harnessed as facile markers to identify polymorphs and crystal orientations of TMDCs.

Universal Oriented van der Waals Epitaxy of 1D Cyanide Chains on Hexagonal 2D Crystals.

The atomic or molecular assembly on 2D materials through the relatively weak van der Waals interaction is quite different from the conventional heteroepitaxy and may result in unique growth behaviors. Here, it is shown that straight 1D cyanide chains display universal epitaxy on hexagonal 2D materials. A universal oriented assembly of cyanide crystals (AgCN, AuCN, and Cu0.5Au0.5CN) is observed, where the chains are aligned along the three zigzag lattice directions of various 2D hexagonal crystals (graphene, h-BN, WS2, MoS2, WSe2, MoSe2, and MoTe2). The potential energy landscape of the hexagonal lattice induces this preferred alignment of 1D chains along the zigzag lattice directions, regardless of the lattice parameter and surface elements as demonstrated by first-principles calculations and parameterized surface potential calculations. Furthermore, the oriented microwires can serve as crystal orientation markers, and stacking-angle-controlled vertical 2D heterostructures are successfully fabricated by using them as markers. The oriented van der Waals epitaxy can be generalized to any hexagonal 2D crystals and will serve as a unique growth process to form crystals with orientations along the zigzag directions by epitaxy.

Fumigant Toxicity of Lamiaceae Plant Essential Oils and Blends of Their Constituents against Adult Rice Weevil Sitophilus oryzae.

To find a new and safe alternative to conventional insecticides, we evaluated the fumigant toxicity of eight Lamiaceae essential oils and their constituents against the adult rice weevil Sitophilus oryzae. Of the eight species tested, hyssop (Hyssopus offcinalis), majoram (Origanum majorana), and Thymus zygis essential oils showed strong fumigant toxicity against S. oryzae adults at 25 mg/L air concentration. Constituents of active essential oils were analyzed by gas chromatography coupled to flame ionization detector (FID) and gas chromatography-mass spectrometry. A total of 13, 15, and 17 compounds were identified from hyssop, majoram, and Thymus zygis essential oils, respectively. Pinocamphone and isopinocamphone were isolated by open column chromatography. Among the test compounds, pinocamphone and isopinocamphone showed the strongest fumigant toxicity against S. oryzae. Sabinene hydrate, linalool, α-terpineol, and terpinen-4-ol exhibited 100% fumigant toxicity against S. oryzae at 3.9 mg/L air concentration. The measured toxicity of the artificial blends of the constituents identified in hyssop, majoram, and Thymus zygis oils indicated that isopinocamphone, terpine-4-ol, and linalool were major contributors to the fumigant toxicity of the artificial blend, respectively.