High-order superlattices by rolling up van der Waals heterostructures.

Two-dimensional (2D) materials1,2 and the associated van der Waals (vdW) heterostructures3-7 have provided great flexibility for integrating distinct atomic layers beyond the traditional limits of lattice-matching requirements, through layer-by-layer mechanical restacking or sequential synthesis. However, the 2D vdW heterostructures explored so far have been usually limited to relatively simple heterostructures with a small number of blocks8-18. The preparation of high-order vdW superlattices with larger number of alternating units is exponentially more difficult, owing to the limited yield and material damage associated with each sequential restacking or synthesis step8-29. Here we report a straightforward approach to realizing high-order vdW superlattices by rolling up vdW heterostructures. We show that a capillary-force-driven rolling-up process can be used to delaminate synthetic SnS2/WSe2 vdW heterostructures from the growth substrate and produce SnS2/WSe2 roll-ups with alternating monolayers of WSe2 and SnS2, thus forming high-order SnS2/WSe2 vdW superlattices. The formation of these superlattices modulates the electronic band structure and the dimensionality, resulting in a transition of the transport characteristics from semiconducting to metallic, from 2D to one-dimensional (1D), with an angle-dependent linear magnetoresistance. This strategy can be extended to create diverse 2D/2D vdW superlattices, more complex 2D/2D/2D vdW superlattices, and beyond-2D materials, including three-dimensional (3D) thin-film materials and 1D nanowires, to generate mixed-dimensional vdW superlattices, such as 3D/2D, 3D/2D/2D, 1D/2D and 1D/3D/2D vdW superlattices. This study demonstrates a general approach to producing high-order vdW superlattices with widely variable material compositions, dimensions, chirality and topology, and defines a rich material platform for both fundamental studies and technological applications.

Highly Robust Room-Temperature Interfacial Ferromagnetism in Ultrathin Co2Si Nanoplates.

The reduced dimensionality and interfacial effects in magnetic nanostructures open the feasibility to tailor magnetic ordering. Here, we report the synthesis of ultrathin metallic Co2Si nanoplates with a total thickness that is tunable to 2.2 nm. The interfacial magnetism coupled with the highly anisotropic nanoplate geometry leads to strong perpendicular magnetic anisotropy and robust hard ferromagnetism at room temperature, with a Curie temperature (TC) exceeding 950 K and a coercive field (HC) > 4.0 T at 3 K and 8750 Oe at 300 K. Theoretical calculations suggest that ferromagnetism originates from symmetry breaking and undercoordinated Co atoms at the Co2Si and SiO2 interface. With protection by the self-limiting intrinsic oxide, the interfacial ferromagnetism of the Co2Si nanoplates exhibits excellent environmental stability. The controllable growth of ambient stable Co2Si nanoplates as 2D hard ferromagnets could open exciting opportunities for fundamental studies and applications in Si-based spintronic devices.

Synthesis of Two-Dimensional MoO2 Nanoplates with Large Linear Magnetoresistance and Nonlinear Hall Effect.

Two-dimensional (2D) materials with large linear magnetoresistance (LMR) are very interesting owing to their potential application in magnetic storage or sensor devices. Here, we report the synthesis of 2D MoO2 nanoplates grown by a chemical vapor deposition (CVD) method and observe large LMR and nonlinear Hall behavior in MoO2 nanoplates. As-obtained MoO2 nanoplates exhibit rhombic shapes and high crystallinity. Electrical studies indicate that MoO2 nanoplates feature a metallic nature with an excellent conductivity of up to 3.7 × 107 S m-1 at 2.5 K. MoO2 nanoplates display a large LMR of up to 455% at 3 K and -9 T. A thickness-dependent LMR analysis suggests that LMR values increase upon increasing the thickness of nanoplates. Besides, nonlinearity has been found in the magnetic-field-dependent Hall resistance, which decreases with increasing temperatures. Our studies highlight that MoO2 nanoplates are promising materials for fundamental studies and potential applications in magnetic storage devices.

Phase-Selective Synthesis of Ultrathin FeTe Nanoplates by Controllable Fe/Te Atom Ratio in the Growth Atmosphere.

Phase controllable synthesis of 2D materials is of significance for tuning related electrical, optical, and magnetic properties. Herein, the phase-controllable synthesis of tetragonal and hexagonal FeTe nanoplates has been realized by a rational control of the Fe/Te ratio in a chemical vapor deposition system. Using density functional theory calculations, it has been revealed that with the change of the Fe/Te ratio, the formation energy of active clusters changes, causing the phase-controllable synthesis of FeTe nanoplates. The thickness of the obtained FeTe nanoplates can be tuned down to the 2D limit (2.8 nm for tetragonal and 1.4 nm for hexagonal FeTe). X-ray diffraction pattern, transmission electron microscopy, and high resolution scanning transmission electron microscope analyses exhibit the high crystallinity of the as-grown FeTe nanoplates. The two kinds of FeTe nanoflakes show metallic behavior and good electrical conductivity, featuring 8.44 × 104 S m-1 for 9.8 nm-thick tetragonal FeTe and 5.45 × 104 S m-1 for 7.6 nm-thick hexagonal FeTe. The study provides an efficient and convenient route for tailoring the phases of FeTe nanoplates, which benefits to study phase-sensitive properties, and may pave the way for the synthesis of other multiphase 2D nanosheets with controllable phases.

Defect Engineering of 2D Semiconductors for Dual Control of Emission and Carrier Polarity.

2D transition metal dichalcogenides (TMDCs) are considered as promising materials in post-Moore technology. However, the low photoluminescence quantum yields (PLQY) and single carrier polarity due to the inevitable defects during material preparation are great obstacles to their practical applications. Here, an extraordinary defect engineering strategy is reported based on first-principles calculations and realize it experimentally on WS2 monolayers by doping with IIIA atoms. The doped samples with large sizes possess both giant PLQY enhancement and effective carrier polarity modulation. Surprisingly, the high PL emission maintained even after one year under ambient environment. Moreover, the constructed p-n homojunctions shows high rectification ratio (≈2200), ultrafast response times and excellent stability. Meanwhile, the doping strategy is universally applicable to other TMDCs and dopants. This smart defect engineering strategy not only provides a general scheme to eliminate the negative influence of defects, but also utilize them to achieve desired optoelectronic properties for multifunctional applications.

Thickness-Dependent Topological Hall Effect in 2D Cr5 Si3 Nanosheets with Noncollinear Magnetic Phase.

Antiferromagnets with noncollinear spin order are expected to exhibit unconventional electromagnetic response, such as spin Hall effects, chiral abnormal, quantum Hall effect, and topological Hall effect. Here, 2D thickness-controlled and high-quality Cr5 Si3 nanosheets that are compatible with the complementary metal-oxide-semiconductor technology are synthesized by chemical vapor deposition method. The angular dependence of electromagnetic transport properties of Cr5 Si3 nanosheets is investigated using a physical property measurement system, and an obvious topological Hall effect (THE) appears at a large tilted magnetic field, which results from the noncollinear magnetic structure of the Cr5 Si3 nanosheet. The Cr5 Si3 nanosheets exhibit distinct thickness-dependent perpendicular magnetic anisotropy (PMA), and the THE only emerges in the specific thickness range with moderate PMA. This work provides opportunities for exploring fundamental spin-related physical mechanisms of noncollinear antiferromagnet in ultrathin limit.

General low-temperature growth of two-dimensional nanosheets from layered and nonlayered materials.

Most of the current methods for the synthesis of two-dimensional materials (2DMs) require temperatures not compatible with traditional back-end-of-line (BEOL) processes in semiconductor industry (450 °C). Here, we report a general BiOCl-assisted chemical vapor deposition (CVD) approach for the low-temperature synthesis of 27 ultrathin 2DMs. In particular, by mixing BiOCl with selected metal powders to produce volatile intermediates, we show that ultrathin 2DMs can be produced at 280-500 °C, which are ~200-300 °C lower than the temperatures required for salt-assisted CVD processes. In-depth characterizations and theoretical calculations reveal the low-temperature processes promoting 2D growth and the oxygen-inhibited synthetic mechanism ensuring the formation of ultrathin nonlayered 2DMs. We demonstrate that the resulting 2DMs exhibit electrical, magnetic and optoelectronic properties comparable to those of 2DMs grown at much higher temperatures. The general low-temperature preparation of ultrathin 2DMs defines a rich material platform for exploring exotic physics and facile BEOL integration in semiconductor industry.

Synthesis of Group VIII Magnetic Transition-Metal-Doped Monolayer MoSe2.

The limitation on the spintronic applications of van der Waals layered transition-metal dichalcogenide semiconductors is ascribed to the intrinsic nonmagnetic feature. Recent studies have proved that substitutional doping is an effective route to alter the magnetic properties of two-dimensional transition-metal dichalcogenides (TMDs). However, highly valid and repeatable substitutional doping of TMDs remains to be developed. Herein, we report group VIII magnetic transition metal-doped molybdenum diselenide (MoSe2) single crystals via a one-pot mixed-salt-intermediated chemical vapor deposition method with high controllability and reproducibility. The high-angle annular dark-field scanning transmission electron microscopy studies further confirm that the sites of Fe are indeed substitutionally incorporated into the MoSe2 monolayer. The Fe-doped MoSe2 monolayer with a concentration from 0.93% to 6.10% could be obtained by controlling the ratios of FeCl3/Na2MoO4. Moreover, this strategy can be extended to create Co(Ni)-doped MoSe2 monolayers. The magnetic hysteresis (M-H) measurements demonstrate that group VIII magnetic transition-metal-doped MoSe2 samples exhibit room-temperature ferromagnetism. Additionally, the Fe-doped MoSe2 field effect transistor shows n-type semiconductor characteristics, indicating the obtainment of a room-temperature dilute magnetic semiconductor. Our approach is universal in magnetic transition-metal substitutional doping of TMDs, and it inspires further research interest in the study of related spintronic and magnetoelectric applications.

Controlled Synthesis of Ultrathin PtSe2 Nanosheets with Thickness-Tunable Electrical and Magnetoelectrical Properties.

Thickness-dependent chemical and physical properties have gained tremendous interest since the emergence of two-dimensional (2D) materials. Despite attractive prospects, the thickness-controlled synthesis of ultrathin nanosheets remains an outstanding challenge. Here, a chemical vapor deposition (CVD) route is reported to controllably synthesize high-quality PtSe2 nanosheets with tunable thickness and explore their thickness-dependent electronic and magnetotransport properties. Raman spectroscopic studies demonstrate all Eg , A1 g , A2 u , and Eu modes are red shift in thicker nanosheets. Electrical measurements demonstrate the 1.7 nm thick nanosheet is a semiconductor with room temperature field-effect mobility of 66 cm2 V-1 s-1 and on/off ratio of 106 . The 2.3-3.8 nm thick nanosheets show slightly gated modulation with high field-effect mobility up to 324 cm2 V-1 s-1 at room-temperature. When the thickness is over 3.8 nm, the nanosheets show metallic behavior with conductivity and breakdown current density up to 6.8 × 105 S m-1 and 6.9 × 107 A cm-2 , respectively. Interestingly, magnetoresistance (MR) studies reveal magnetic orders exist in this intrinsically non-magnetic material system, as manifested by the thickness-dependent Kondo effect, where both metal to insulator transition and negative MR appear upon cooling. Together, these studies suggest that PtSe2 is an intriguing system for both developing novel functional electronics and conducting fundamental 2D magnetism study.