Two-dimensional Van Der Waals Crystals Research Articles

Probing the Band Splitting near the Γ Point in the van der Waals Magnetic Semiconductor CrSBr.

This study investigates the electronic band structure of chromium sulfur bromide (CrSBr) through comprehensive photoluminescence (PL) characterization. We clearly identify low-temperature optical transitions between two closely adjacent conduction-band states and two different valence-band states. The analysis on the PL data robustly unveils energy splittings, band gaps, and excitonic transitions across different thicknesses of CrSBr, from monolayer to bulk. Temperature-dependent PL measurements elucidate the stability of the band splitting below the Néel temperature, suggesting that magnons coupled with excitons are responsible for the symmetry breaking and brightening of the transitions from the secondary conduction band minimum (CBM2) to the global valence band maximum (VBM1). Collectively, these results not only reveal splitting in both the conduction and valence bands but also highlight a significant advance in our understanding of the interplay between the optical, electronic, and magnetic properties of antiferromagnetic two-dimensional van der Waals crystals.

Dual-band high quality-factor perfect absorber based on uniaxial/biaxial anisotropic van der Waals polar crystals

Phonon polaritons (PhPs) in two-dimensional van der Waals crystals, such as hexagonal boron nitride (hBN) and α-phase molybdenum trioxide (α-MoO3), exhibit remarkable spatial confinement and extremely low optical losses, offering possibilities for the development of novel micro and nanophotonic devices at mid-infrared wavelengths. Here, we demonstrate the potential of the proposed Tamm structure to achieve dual-band high quality-factor perfect absorption within the mid-infrared range. This structure utilizes upper and lower spacer layers to isolate the anisotropic materials hBN and α-MoO3 from one-dimensional photonic crystals, where the Tamm phonon polaritons (TPhPs) are respectively excited at the interfaces, facilitating strong coupling with incident light and leading to significant dual-band perfect absorption phenomena. The results demonstrate that due to polariton resonances, the absorption peaks exhibit extremely narrow absorption bandwidths, with the maximum quality-factor reaching up to 297. In addition, tunable resonant wavelengths and polarization-dependent absorption properties are also demonstrated in the proposed Tamm structure. This study provides an alternative and straightforward approach for constructing dynamic and multifunctional optical devices such as optical modulators, tunable multi-band filters and biosensors.

High-κ van der Waals Oxide MoO3 as Efficient Gate Dielectric for MoS2 Field-Effect Transistors.

Two-dimensional van der Waals crystals (2D vdW) are recognized as one of the potential materials to solve the physical limits caused by size scaling. Here, vdW metal oxide MoO3 is applied with the gate dielectric in a 2D field-effect transistor (FET). Due to its high dielectric constant and the good response of MoS2 to visible light, we obtained a field effect transistor for photodetection. In general, the device exhibits a threshold voltage near 0 V, Ion/Ioff ratio of 105, electron mobility about 85 cm2 V−1 s−1 and a good response to visible light, the responsivity is near 5 A/W at low laser power, which shows that MoO3 is a potential material as gate dielectric.

Two-dimensional van der Waals: Characterization and manipulation of superconductivity

Superconductivity has become a fascinating research field in condensed matter physics since its discovery in 1911. Nowadays, two-dimensional materials exhibit a variety of new physical phenomena, such as Ising superconductivity, topological superconductivity, and unconventional superconductivity. A number of two-dimensional van der Waals crystals exhibit superconductivity, which provide us with a broad research platform for exploring various physical effects and novel phenomena. In this review, we focus our attention on superconducting properties of two-dimensional van der Waals crystals, and highlight the recent progress of the state-of-the-art research on synthesis, characterization, and isolation of single and few layer nanosheets and the assembly of two-dimensional van der Waals superconductors. Finally we conclude the future research directions and prospects in two-dimensional materials with superconductivity.

Tunable room-temperature ferromagnetism in Co-doped two-dimensional van der Waals ZnO

The recent discovery of ferromagnetism in two-dimensional van der Waals crystals has provoked a surge of interest in the exploration of fundamental spin interaction in reduced dimensions. However, existing material candidates have several limitations, notably lacking intrinsic room-temperature ferromagnetic order and air stability. Here, motivated by the anomalously high Curie temperature observed in bulk diluted magnetic oxides, we demonstrate room-temperature ferromagnetism in Co-doped graphene-like Zinc Oxide, a chemically stable layered material in air, down to single atom thickness. Through the magneto-optic Kerr effect, superconducting quantum interference device and X-ray magnetic circular dichroism measurements, we observe clear evidences of spontaneous magnetization in such exotic material systems at room temperature and above. Transmission electron microscopy and atomic force microscopy results explicitly exclude the existence of metallic Co or cobalt oxides clusters. X-ray characterizations reveal that the substitutional Co atoms form Co2+ states in the graphitic lattice of ZnO. By varying the Co doping level, we observe transitions between paramagnetic, ferromagnetic and less ordered phases due to the interplay between impurity-band-exchange and super-exchange interactions. Our discovery opens another path to 2D ferromagnetism at room temperature with the advantage of exceptional tunability and robustness.

Van der Waals epitaxial growth of air-stable CrSe2 nanosheets with thickness-tunable magnetic order.

The discovery of intrinsic ferromagnetism in ultrathin two-dimensional van der Waals crystals opens up exciting prospects for exploring magnetism in the ultimate two-dimensional limit. Here, we show that environmentally stable CrSe2 nanosheets can be readily grown on a dangling-bond-free WSe2 substrate with systematically tunable thickness down to the monolayer limit. These CrSe2/WSe2 heterostructures display high-quality van der Waals interfaces with well-resolved moiré superlattices and ferromagnetic behaviour. We find no apparent change in surface roughness or magnetic properties after months of exposure in air. Our calculations suggest that charge transfer from the WSe2 substrate and interlayer coupling within CrSe2 play a critical role in the magnetic order in few-layer CrSe2 nanosheets. The highly controllable growth of environmentally stable CrSe2 nanosheets with tunable thickness defines a robust two-dimensional magnet for fundamental studies and potential applications in magnetoelectronic and spintronic devices.

Polariton waveguide modes in two-dimensional van der Waals crystals: an analytical model and correlative nano-imaging

Two-dimensional van der Waals (vdW) crystals can sustain various types of polaritons with strong electromagnetic confinements, making them highly attractive for nanoscale photonic and optoelectronic applications. While extensive experimental and numerical studies have been devoted to the polaritons of the vdW crystals, analytical models are sparse. Particularly, applying the model to describe polariton behaviors that are visualized by state of the art near-field optical microscopy requires further investigations. In this study, we develop an analytical waveguide model to describe polariton propagations in vdW crystals. The dispersion contours, dispersion relations, and localized electromagnetic field distributions of polariton waveguide modes are derived. The model is verified by real-space optical nano-imaging and numerical simulation of phonon polaritons in α-MoO3, which is a vdW biaxial crystal. Although we focus on α-MoO3, the proposed model is valid for other polaritonic crystals within the vdW family given the corresponding dielectric substitutions. Our model therefore provides an analytical rationale for describing and understanding the localized electromagnetic fields in vdW crystals that are associated with polaritons.

Humidity effect on peeling of monolayer graphene and hexagonal boron nitride

Ambient humidity introduces water adsorption and intercalation at the surfaces and interfaces of low-dimensional materials. Our extensive molecular dynamics (MD) simulations reveal the completely opposite contributions of interfacial water to the peeling of monolayer graphene and hexagonal boron nitride (h-BN) sheets from graphite and BN substrates. For graphene, interfacial water decreases the peeling force, due to lower adhesion at the graphene/water interface. The peeling force of h-BN increases with an increase in the thickness of interfacial water, owing to stronger adhesion at the h-BN/water interface and the detachment of the water layer from the substrates. In this work, a theoretical model considering graphene/water and water/substrate interfacial adhesion energies is established, to predict the peeling forces of graphene and h-BN, which coincides well with the peeling forces predicted by the MD simulations. Our results should provide a deeper insight into the effect of interfacial water, induced by ambient humidity, on mechanical exfoliation and the transfer of two-dimensional van der Waals crystals.

Semimetallic features in thermoelectric transport properties of 2H–3R phase niobium diselenide

Abstract In two-dimensional van der Waals crystals, the interlayer stacking sequence often leads to a change in crystal symmetry and, thus, new polymorphs, leading to an abundant array of physical properties. In this paper, we report the polymorphic form of 2H–3R–NbSe2 that exhibits a substantial difference in terms of the gate dependence of semimetallic behavior and Seebeck coefficient, compared to the well-known 2H–NbSe2 with metallic transport behavior. The semimetallic features of 2H–3R–NbSe2 indicate the presence of minor carriers, confirmed through theoretical calculations, which is in good agreement with the transport behavior. Our results reveal perspectives for understanding the metastable 2H–3R phase NbSe2, which is not far from equilibrium, and for engineering the materials necessary for efficient energy harvesting.

Switching 2D magnetic states via pressure tuning of layer stacking.

The physical properties of two-dimensional van der Waals crystals can be sensitive to interlayer coupling. For two-dimensional magnets1-3, theory suggests that interlayer exchange coupling is strongly dependent on layer separation while the stacking arrangement can even change the sign of the interlayer magnetic exchange, thus drastically modifying the ground state4-10. Here, we demonstrate pressure tuning of magnetic order in the two-dimensional magnet CrI3. We probe the magnetic states using tunnelling8,11-13 and scanning magnetic circular dichroism microscopy measurements2. We find that interlayer magnetic coupling can be more than doubled by hydrostatic pressure. In bilayer CrI3, pressure induces a transition from layered antiferromagnetic to ferromagnetic phase. In trilayer CrI3, pressure can create coexisting domains of three phases, one ferromagnetic and two antiferromagnetic. The observed changes in magnetic order can be explained by changes in the stacking arrangement. Such coupling between stacking order and magnetism provides ample opportunities for designer magnetic phases and functionalities.

Gate-tunable room-temperature ferromagnetism in two-dimensional Fe3GeTe2

Materials research has driven the development of modern nano-electronic devices. In particular, research in magnetic thin films has revolutionized the development of spintronic devices1,2 because identifying new magnetic materials is key to better device performance and design. Van der Waals crystals retain their chemical stability and structural integrity down to the monolayer and, being atomically thin, are readily tuned by various kinds of gate modulation3,4. Recent experiments have demonstrated that it is possible to obtain two-dimensional ferromagnetic order in insulating Cr2Ge2Te6 (ref. 5) and CrI3 (ref. 6) at low temperatures. Here we develop a device fabrication technique and isolate monolayers from the layered metallic magnet Fe3GeTe2 to study magnetotransport. We find that the itinerant ferromagnetism persists in Fe3GeTe2 down to the monolayer with an out-of-plane magnetocrystalline anisotropy. The ferromagnetic transition temperature, Tc, is suppressed relative to the bulk Tc of 205 kelvin in pristine Fe3GeTe2 thin flakes. An ionic gate, however, raises Tc to room temperature, much higher than the bulk Tc. The gate-tunable room-temperature ferromagnetism in two-dimensional Fe3GeTe2 opens up opportunities for potential voltage-controlled magnetoelectronics7-11 based on atomically thin van der Waals crystals.

Reversible Tuning of the Ferromagnetic Behavior in Mn-Doped MoS2 Nanosheets via Interface Charge Transfer.

Reversible manipulation of the magnetic behavior of two-dimensional van der Waals crystals is crucial for expanding their applications in spin-based information-processing technologies. However, to date, most experimental approaches to tune the magnetic properties are single way and have very limited practical applications. Here, we report an interface charge-transfer method for obtaining a reversible and air-stable magnetic response at room temperature in Mn-doped MoS2 nanosheets. By adsorption of benzyl viologen (BV) molecules as the charge donor, the saturation magnetization of Mn-doped MoS2 nanosheets is enhanced by a magnitude of 60%, and the magnetization can be restored to the original value when the adsorbed BV molecules are removed. This cycle can be repeated many times on the same sample without detectable degradation. Experimental characterizations and first-principles calculations suggest that the enhanced magnetization can be attributed to the increase of Mn magnetic moment because of the enriched electrons transferred from BV molecules. This work shows that interface charge transfer may open up a new pathway for reversibly tuning the exchange interactions in two-dimensional nanostructures.

Hubbard Model Physics in Transition Metal Dichalcogenide Moiré Bands.

Flexible long period moiré superlattices form in two-dimensional van der Waals crystals containing layers that differ slightly in lattice constant or orientation. In this Letter we show theoretically that isolated flat moiré bands described by generalized triangular lattice Hubbard models are present in twisted transition metal dichalcogenide heterobilayers. The hopping and interaction strength parameters of the Hubbard model can be tuned by varying the twist angle and the three-dimensional dielectric environment. When the flat moiré bands are partially filled, candidate many-body ground states at some special filling factors include spin-liquid states, quantum anomalous Hall insulators, and chiral d-wave superconductors.

Towards properties on demand in quantum materials.

The past decade has witnessed an explosion in the field of quantum materials, headlined by the predictions and discoveries of novel Landau-symmetry-broken phases in correlated electron systems, topological phases in systems with strong spin-orbit coupling, and ultra-manipulable materials platforms based on two-dimensional van der Waals crystals. Discovering pathways to experimentally realize quantum phases of matter and exert control over their properties is a central goal of modern condensed-matter physics, which holds promise for a new generation of electronic/photonic devices with currently inaccessible and likely unimaginable functionalities. In this Review, we describe emerging strategies for selectively perturbing microscopic interaction parameters, which can be used to transform materials into a desired quantum state. Particular emphasis will be placed on recent successes to tailor electronic interaction parameters through the application of intense fields, impulsive electromagnetic stimulation, and nanostructuring or interface engineering. Together these approaches outline a potential roadmap to an era of quantum phenomena on demand.

Discovery of intrinsic ferromagnetism in two-dimensional van der Waals crystals.

The realization of long-range ferromagnetic order in two-dimensional van der Waals crystals, combined with their rich electronic and optical properties, could lead to new magnetic, magnetoelectric and magneto-optic applications. In two-dimensional systems, the long-range magnetic order is strongly suppressed by thermal fluctuations, according to the Mermin-Wagner theorem; however, these thermal fluctuations can be counteracted by magnetic anisotropy. Previous efforts, based on defect and composition engineering, or the proximity effect, introduced magnetic responses only locally or extrinsically. Here we report intrinsic long-range ferromagnetic order in pristine Cr2Ge2Te6 atomic layers, as revealed by scanning magneto-optic Kerr microscopy. In this magnetically soft, two-dimensional van der Waals ferromagnet, we achieve unprecedented control of the transition temperature (between ferromagnetic and paramagnetic states) using very small fields (smaller than 0.3 tesla). This result is in contrast to the insensitivity of the transition temperature to magnetic fields in the three-dimensional regime. We found that the small applied field leads to an effective anisotropy that is much greater than the near-zero magnetocrystalline anisotropy, opening up a large spin-wave excitation gap. We explain the observed phenomenon using renormalized spin-wave theory and conclude that the unusual field dependence of the transition temperature is a hallmark of soft, two-dimensional ferromagnetic van der Waals crystals. Cr2Ge2Te6 is a nearly ideal two-dimensional Heisenberg ferromagnet and so will be useful for studying fundamental spin behaviours, opening the door to exploring new applications such as ultra-compact spintronics.