vdW Crystals Research Articles

Van der Waals ferromagnetic Josephson junctions

Superconductor-ferromagnet interfaces in two-dimensional heterostructures present a unique opportunity to study the interplay between superconductivity and ferromagnetism. The realization of such nanoscale heterostructures in van der Waals (vdW) crystals remains largely unexplored due to the challenge of making atomically-sharp interfaces from their layered structures. Here, we build a vdW ferromagnetic Josephson junction (JJ) by inserting a few-layer ferromagnetic insulator Cr2Ge2Te6 into two layers of superconductor NbSe2. The critical current and corresponding junction resistance exhibit a hysteretic and oscillatory behavior against in-plane magnetic fields, manifesting itself as a strong Josephson coupling state. Also, we observe a central minimum of critical current in some JJ devices as well as a nontrivial phase shift in SQUID structures, evidencing the coexistence of 0 and π phase in the junction region. Our study paves the way to exploring sensitive probes of weak magnetism and multifunctional building-blocks for phase-related superconducting circuits using vdW heterostructures.

Large-Area Epitaxial Film Growth of van der Waals Ferromagnetic Ternary Chalcogenides.

Following the first experimental realization of intrinsic ferromagnetism in 2D van der Waals (vdW) crystals, several ternary metal chalcogenides with unprecedented long-range ferromagnetic order have been explored. However, the synthesis of large-area 2D ternary metal chalcogenide thin films is a great challenge, and a generalized synthesis has not been demonstrated yet. Here, a quick and scalable synthesis of epitaxially aligned ferromagnetic ternary metal chalcogenide thin films (Cr2 Ge2 Te6 , Cr2 Si2 Te6 , Mn3 Si2 Te6 ) is reported. The synthesis is based on the flux-controlled surface diffusion of Te on metal (Cr, Mn)-deposited wafer (Ge, Si) substrates. Magnetic anisotropy study of the epitaxial ternary thin films reveals the intrinsic magnetic easy axis; out-of-plane direction for Cr2 Ge2 Te6 and Cr2 Si2 Te6 , and in-plane direction for Mn3 Si2 Te6 . In addition to the synthesis, this work creates an opportunity for transfer-free device fabrication for realizing magnetoelectronics based on the electrical control of both charge and spin degrees of freedom in 2D ferromagnetic semiconductors.

Nondestructive Picosecond Ultrasonic Probing of Intralayer and van der Waals Interlayer Bonding in α‐ and β‐In2Se3

AbstractThe interplay between the strong intralayer covalent‐ionic bonds and the weak interlayer van der Waals (vdW) forces between the neighboring layers of vdW crystals gives rise to unique physical and chemical properties. Here, the intralayer and interlayer bondings in α and β polytypes of In2Se3 are studied, a vdW material with potential applications in advanced electronic and optical devices. Picosecond ultrasonic experiments are conducted to probe the sound velocity in the direction perpendicular to the vdW layers. The measured sound velocities are different in α‐ and β‐In2Se3, suggesting a significant difference in their elastic properties. Density functional theory and an effective spring model are used to calculate the elastic stiffness of the layer and vdW gap in α‐ and β‐In2Se3. The calculated elastic moduli show good agreement with experimental values and reveal the dominant contribution of interlayer atomic bonding to the different elastic properties of the two polytypes. The findings show the power of picosecond ultrasonics for probing the fundamental elastic properties of vdW materials. The data and analysis also provide a reliable description of the intra‐ and interlayer forces in complex crystal structures, such as the polytype phases of In2Se3.

Interfacial Friction Anisotropy in Few-Layer Van der Waals Crystals.

Friction anisotropy is one of the important friction behaviors for two-dimensional (2D) van der Waals (vdW) crystals. The effects of normal pressure and thickness on the interfacial friction anisotropy in few-layer graphene, h-BN, and MoSe2 under constant normal force mode have been extensively investigated by first-principle calculations. The increase of normal pressure and layer number enhances the interfacial friction anisotropy for graphene and h-BN but weakens that for MoSe2. Such significant deviations in the interfacial friction anisotropy of few-layer graphene, h-BN and MoSe2 can be mainly attributed to the opposite contributions of electron kinetic energies and electrostatic energies to the sliding energy barriers and different interlayer charge exchanges. Our results deepen the understanding of the influence of external loading and thickness on the friction properties of 2D vdW crystals.

Van der Waals electride: Toward intrinsic two-dimensional ferromagnetism of spin-polarized anionic electrons

Discoveries of two-dimensional (2D) magnetism originated from confined atomic layers in van der Waals (vdW) crystals provide an interesting arena for elucidating its fundamentals and enrich magneto-electric and quantum properties. However, a material that exhibits intrinsic 2D magnetism of interstitial electrons occupying layered space, as a root system of magnetic vdW crystals, remains obscure. In this work, 2D ferromagnetic vdW electride, [RECl]2+·2e− (RE = Y and La) is reported with perfectly isolated ferromagnetic 2D blocks encompassing quasi-atomic electron layers. The ferromagnetism of the vdW electride with Curie temperature of 100 K originates from the spin-polarized quasi-atomic electrons with a substantial moment up to ∼0.91 Bohr magneton, which behave as magnetic elements in paramagnetic lattice framework. Invariable ferromagnetism at the monolayer limit strongly supports the 2D ferromagnetism of quasi-atomic electrons. These findings expand the variety of 2D magnetic crystals, providing a promising platform to study the emergent magnetism of low-dimensional electron phases.

Strain, Doping, and Electronic Transport of Large Area Monolayer MoS2 Exfoliated on Gold and Transferred to an Insulating Substrate.

Gold-assisted mechanical exfoliation currently represents a promising method to separate ultralarge (centimeter scale) transition metal dichalcogenide (TMD) monolayers (1L) with excellent electronic and optical properties from the parent van der Waals (vdW) crystals. The strong interaction between Au and chalcogen atoms is key to achieving this nearly perfect 1L exfoliation yield. On the other hand, it may significantly affect the doping and strain of 1L TMDs in contact with Au. In this paper, we systematically investigated the morphology, strain, doping, and electrical properties of large area 1L MoS2 exfoliated on ultraflat Au films (0.16–0.21 nm roughness) and finally transferred to an insulating Al2O3 substrate. Raman mapping and correlative analysis of the E′ and A1′ peak positions revealed a moderate tensile strain (ε ≈ 0.2%) and p-type doping (n ≈ −0.25 × 1013 cm–2) of 1L MoS2 in contact with Au. Nanoscale resolution current mapping and current–voltage (I–V) measurements by conductive atomic force microscopy (C-AFM) showed direct tunneling across the 1L MoS2 on Au, with a broad distribution of tunneling barrier values (ΦB from 0.7 to 1.7 eV) consistent with p-type doping of MoS2. After the final transfer of 1L MoS2 on Al2O3/Si, the strain was converted to compressive strain (ε ≈ −0.25%). Furthermore, an n-type doping (n ≈ 0.5 × 1013 cm–2) was deduced by Raman mapping and confirmed by electrical measurements of an Al2O3/Si back-gated 1L MoS2 transistor. These results provide a deeper understanding of the Au-assisted exfoliation mechanism and can contribute to its widespread application for the realization of novel devices and artificial vdW heterostructures.

Charge Carrier Transport in Van Der Waals Semiconductor InSe Intercalated with RbNO3 Probed by Direct Current Methods

Layered van der Waals (vdW) semiconductors show great promise to overcome limitations imposed by traditional semiconductor materials. The synergistic combination of vdW semiconductors with other functional materials can offer novel working principles and device concepts for future nano- and optoelectronics. Herein, we investigate the influence of the intercalation of semiconducting n-type InSe vdW crystals with ferroelectric rubidium nitrate (RbNO3) on the transport of charge carriers along and across the layers. The apparent maxima in the temperature dependences of the Hall coefficient are explained in the framework of a model that predicts, along with three-dimensional carriers, the existence of two-dimensional ones contributing only to the conductivity along the layers. The revealed increase of the conductivity anisotropy and its activation variation with temperature, which is mainly due to a decrease of the conductivity across the layers, confirm a two-dimensionalization of electron gas in n-InSe after insertion of the ferroelectric. From the numerical analysis, we determined the densities of carriers of both types, concentrations of donors and acceptors, as well as the value of the interlayer barrier.

Temperature-Dependent Phonon Shifts in van der Waals Crystals.

In recent years, there has been an explosive increase in the research on van der Waals (vdW) crystals because of their great potential applications in many optoelectronic devices. It is necessary to determine their temperature-dependent lattice vibration characteristics because their thermal and electrical transport are closely related to the anharmonic phonon effect, which will affect the performance of the devices. We review the temperature-dependent Raman spectroscopy of vdW crystals, systematically introduce the thermal behavior of optical phonons, and summarize their shift with temperature. Upon analyzing the theoretical models and summarizing the reported experimental data, it is found that the phonon shifts of vdW crystals have a "quasi-linear" relationship with temperature, which is widely described with first-order temperature (FOT) coefficients obtained through a linear fit. Thus, subsequently, the phonon shifts of monolayer materials, different-thickness crystals, suspended and supported samples, in-plane and out-of-plane modes in the same vdW materials, as well as heterostructures and alloys are discussed through comparative analysis of FOT coefficients.

Van der Waals Phonon Polariton Microstructures for Configurable Infrared Electromagnetic Field Localizations

AbstractPolar van der Waals (vdW) crystals that support phonon polaritons have recently attracted much attention because they can confine infrared and terahertz (THz) light to deeply subwavelength dimensions, allowing for the guiding and manipulation of light at the nanoscale. The practical applications of these crystals in devices rely strongly on deterministic engineering of their spatially localized electromagnetic field distributions, which has remained challenging. The polariton interference can be enhanced and tailored by patterning the vdW crystal α‐MoO3 into microstructures that support highly in‐plane anisotropic phonon polaritons. The orientation of the polaritonic in‐plane isofrequency curve relative to the microstructure edges is a critical parameter governing the polariton interference, rendering the configuration of infrared electromagnetic field localizations by enabling the tuning of the microstructure size and shape and the excitation frequency. Thus, the study presents an effective rationale for engineering infrared light flow in planar photonic devices.

Mechanical exfoliation of large area 2D materials from vdW crystals

Monolayer two-dimensional (2D) materials, such as graphene and transition metal dichalcogenides (TMDCs), provide a versatile platform for exploring novel physical phenomena at the 2D limit, and show great promise for next-generation electronic, optoelectronic, and quantum devices. To overcome the weak van der Waals interaction in the bulk layered crystal and achieve high quality single-crystal monolayers is a crucial task in top-down mechanical exfoliation. Tape exfoliation has long been the dominant approach to obtain single-crystal monolayers with high quality. More recently, there has been a fast development of using metals as an intermediate to enhance monolayer area and exfoliation yield. This review will provide a survey of mechanical exfoliation strategies of tape and metal-assisted exfoliations, particularly for the most popular graphene and TMDC materials. The interfacial interaction and lateral strain between monolayer and other materials such as oxides and metals play a crucial role in monolayer selectivity and yield. The challenges and opportunities will be highlighted for future development of exfoliating procedures to achieve large-area and high-quality 2D material monolayers and artificial stacks.

Mid infrared polarization engineering via sub-wavelength biaxial hyperbolic van der Waals crystals

Mid-infrared (IR) spectral region is of immense importance for astronomy, medical diagnosis, security and imaging due to the existence of the vibrational modes of many important molecules in this spectral range. Therefore, there is a particular interest in miniaturization and integration of IR optical components. To this end, 2D van der Waals (vdW) crystals have shown great potential owing to their ease of integration with other optoelectronic platforms and room temperature operation. Recently, 2D vdW crystals of alpha-hbox {MoO}_{3} and alpha-hbox {V}_2 hbox {O}_5 have been shown to possess the unique phenomenon of natural in-plane biaxial hyperbolicity in the mid-infrared frequency regime at room temperature. Here, we report a unique application of this in-plane hyperbolicity for designing highly efficient, lithography free and extremely subwavelength mid-IR photonic devices for polarization engineering. In particular, we show the possibility of a significant reduction in the device footprint while maintaining an enormous extinction ratio from alpha-hbox {MoO}_{3} and alpha-hbox {V}_2hbox {O}_5 based mid-IR polarizers. Furthermore, we investigate the application of sub-wavelength thin films of these vdW crystals towards engineering the polarization state of incident mid-IR light via precise control of polarization rotation, ellipticity and relative phase. We explain our results using natural in-plane hyperbolic anisotropy of alpha-hbox {MoO}_{3} and alpha-hbox {V}_2hbox {O}_5 via both analytical and full-wave electromagnetic simulations. This work provides a lithography free alternative for miniaturized mid-infrared photonic devices using the hyperbolic anisotropy of alpha-hbox {MoO}_{3} and alpha-hbox {V}_2hbox {O}_5.

Scalable Van der Waals Two-Dimensional PtTe2 Layers Integrated onto Silicon for Efficient Near-to-Mid Infrared Photodetection.

In recent years, there has been increasing interest in leveraging two-dimensional (2D) van der Waals (vdW) crystals for infrared (IR) photodetection, exploiting their unusual optoelectrical properties. Some 2D vdW materials with small band gap energies such as graphene and black phosphorus have been explored as stand-alone IR responsive layers in photodetectors. However, the devices incorporating these IR-sensitive 2D layers often exhibited poor performances owing to their preparation issues such as limited scalability and air instability. Herein, we explored wafer-scale 2D platinum ditelluride (PtTe2) layers for near-to-mid IR photodetection by directly growing them onto silicon (Si) wafers. 2D PtTe2/Si heterojunctions exhibited wavelength- and intensity-dependent high photocurrents in a spectral range of ∼1-7 μm, significantly outperforming stand-alone 2D PtTe2 layers. The observed superiority is attributed to their excellent Schottky junction characteristics accompanying suppressed carrier recombination as well as optical absorbance competition between 2D PtTe2 layers and Si. The direct and scalable growth of 2D PtTe2 layers was further extended to demonstrate mechanically flexible IR photodetectors.

Integrating van der Waals materials on paper substrates for electrical and optical applications

Paper holds the promise to replace silicon substrates in applications like internet of things or disposable electronics that require ultra-low-cost electronic components and an environmentally friendly electronic waste management. In the last years, spurred by the abovementioned properties of paper as a substrate and the exceptional electronic, mechanical and optical properties of van der Waals (vdW) materials, many research groups have worked towards the integration of vdW materials-based devices on paper. Recently, a method to deposit a continuous film of densely packed interconnects of vdW materials on paper by simply rubbing the vdW crystals against the rough surface of paper has been presented. This method utilizes the weak interlayer vdW interactions and allows cleaving of the crystals into micro platelets through the abrasion against the paper. Here, we aim to illustrate the general character and the potential of this technique by fabricating films of 39 different vdW materials (including superconductors, semi-metals, semiconductors, and insulators) on standard copy paper. We have thoroughly characterized their optical properties showing their high optical quality: one can easily resolve the absorption band edge of semiconducting vdW materials and even the excitonic features present in some vdW materials with high exciton binding energy. We also measured the electrical resistivity for several vdW materials films on paper finding exceptionally low values, which are in some cases, orders of magnitude lower than those reported for analogous films produced by inkjet printing. We finally demonstrate the fabrication of field-effect devices with vdW materials on paper using the paper substrate as an ionic gate.

Ultrafast non-excitonic valley Hall effect in MoS2/WTe2 heterobilayers

The valley Hall effect (VHE) in two-dimensional (2D) van der Waals (vdW) crystals is a promising approach to study the valley pseudospin. Most experiments so far have used bound electron-hole pairs (excitons) through local photoexcitation. However, the valley depolarization of such excitons is fast, so that several challenges remain to be resolved. We address this issue by exploiting a unipolar VHE using a heterobilayer made of monolayer MoS2/WTe2 to exhibit a long valley-polarized lifetime due to the absence of electron-hole exchange interaction. The unipolar VHE is manifested by reduced photoluminescence at the MoS2 A exciton energy. Furthermore, we provide quantitative information on the time-dependent valley Hall dynamics by performing the spatially-resolved ultrafast Kerr-rotation microscopy; we find that the valley-polarized electrons persist for more than 4 nanoseconds and the valley Hall mobility exceeds 4.49 × 103 cm2/Vs, which is orders of magnitude larger than previous reports.

Néel-type skyrmions and their current-induced motion in van der Waals ferromagnet-based heterostructures

Since the discovery of ferromagnetic two-dimensional (2D) van der Waals (vdW) crystals, significant interest on such 2D magnets has emerged, inspired by their appealing properties and integration with other 2D family for unique heterostructures. In known 2D magnets, spin-orbit coupling (SOC) stabilizes perpendicular magnetic anisotropy (PMA). Such a strong SOC could also lift the chiral degeneracy, leading to the formation of topological magnetic textures such as skyrmions through the Dzyaloshinskii-Moriya interaction (DMI). Here, we report the experimental observation of N\'eel-type chiral magnetic skyrmions and their lattice (SkX) formation in a vdW ferromagnet Fe3GeTe2 (FGT). We demonstrate the ability to drive individual skyrmion by short current pulses along a vdW heterostructure, FGT/h-BN, as highly required for any skyrmion-based spintronic device. Using first principle calculations supported by experiments, we unveil the origin of DMI being the interfaces with oxides, which then allows us to engineer vdW heterostructures for desired chiral states. Our finding opens the door to topological spin textures in the 2D vdW magnet and their potential device application.

Extracting the Infrared Permittivity of SiO2 Substrates Locally by Near-Field Imaging of Phonon Polaritons in a van der Waals Crystal.

Layered materials in which individual atomic layers are bonded by weak van der Waals forces (vdW materials) constitute one of the most prominent platforms for materials research. Particularly, polar vdW crystals, such as hexagonal boron nitride (h-BN), alpha-molybdenum trioxide (α-MoO3) or alpha-vanadium pentoxide (α-V2O5), have received significant attention in nano-optics, since they support phonon polaritons (PhPs)―light coupled to lattice vibrations― with strong electromagnetic confinement and low optical losses. Recently, correlative far- and near-field studies of α-MoO3 have been demonstrated as an effective strategy to accurately extract the permittivity of this material. Here, we use this accurately characterized and low-loss polaritonic material to sense its local dielectric environment, namely silica (SiO2), one of the most widespread substrates in nanotechnology. By studying the propagation of PhPs on α-MoO3 flakes with different thicknesses laying on SiO2 substrates via near-field microscopy (s-SNOM), we extract locally the infrared permittivity of SiO2. Our work reveals PhPs nanoimaging as a versatile method for the quantitative characterization of the local optical properties of dielectric substrates, crucial for understanding and predicting the response of nanomaterials and for the future scalability of integrated nanophotonic devices.

Light-Tunable Ferromagnetism in Atomically Thin Fe_{3}GeTe_{2} Driven by Femtosecond Laser Pulse.

The recent discovery of intrinsic ferromagnetism in two-dimensional (2D) van der Waals (vdW) crystals has opened up a new arena for spintronics, raising an opportunity of achieving tunable intrinsic 2D vdW magnetism. Here, we show that the magnetization and the magnetic anisotropy energy (MAE) of few-layered Fe_{3}GeTe_{2} (FGT) is strongly modulated by a femtosecond laser pulse. Upon increasing the femtosecond laser excitation intensity, the saturation magnetization increases in an approximately linear way and the coercivity determined by the MAE decreases monotonically, showing unambiguously the effect of the laser pulse on magnetic ordering. This effect observed at room temperature reveals the emergence of light-driven room-temperature (300K) ferromagnetism in 2D vdW FGT, as its intrinsic Curie temperature T_{C} is ∼200 K. The light-tunable ferromagnetism is attributed to the changes in the electronic structure due to the optical doping effect. Our findings pave a novel way to optically tune 2D vdW magnetism and enhance the T_{C} up to room temperature, promoting spintronic applications at or above room temperature.

Publisher Correction: Real-space observation of vibrational strong coupling between propagating phonon polaritons and organic molecules

Phonon polaritons (PPs) in van der Waals (vdW) materials can strongly enhance light-matter interactions at mid-infrared frequencies, owing to their extreme infrared field confinement and long lifetimes. PPs thus bear potential for achieving vibrational strong coupling (VSC) with molecules. Although the onset of VSC has recently been observed spectroscopically with PP nanoresonators, no experiments so far have resolved VSC in real space and with propagating modes in unstructured layers. Here, we demonstrate by real-space nanoimaging that VSC can be achieved between propagating PPs in thin vdW crystals (specifically h-BN) and molecular vibrations in adjacent thin molecular layers. To that end, we performed near-field polariton interferometry, showing that VSC leads to the formation of a propagating hybrid mode with a pronounced anti-crossing region in its dispersion, in which propagation with negative group velocity is found. Numerical calculations predict VSC for nanometer-thin molecular layers and PPs in few-layer vdW materials, which could make propagating PPs a promising platform for ultra-sensitive on-chip spectroscopy and strong coupling experiments.

Nanoscale-Confined Terahertz Polaritons in a van der Waals Crystal.

Electromagnetic field confinement is crucial for nanophotonic technologies, since it allows for enhancing light-matter interactions, thus enabling light manipulation in deep sub-wavelength scales. In the terahertz (THz) spectral range, radiation confinement is conventionally achieved with specially designed metallic structures-such as antennas or nanoslits-with large footprints due to the rather long wavelengths of THz radiation. In this context, phonon polaritons-light coupled to lattice vibrations-in van der Waals (vdW) crystals have emerged as a promising solution for controlling light beyond the diffraction limit, as they feature extreme field confinements and low optical losses. However, experimental demonstration of nanoscale-confined phonon polaritons at THz frequencies has so far remained elusive. Here, it is provided by employing scattering-type scanning near-field optical microscopy combined with a free-electron laser to reveal a range of low-loss polaritonic excitations at frequencies from 8 to 12 THz in the vdW semiconductor α-MoO3 . In this study, THz polaritons are visualized with: i) in-plane hyperbolic dispersion, ii) extreme nanoscale field confinement (below λo ⁄75), and iii) long polariton lifetimes, with a lower limit of >2ps.

Quantitative Nanoinfrared Spectroscopy of Anisotropic van der Waals Materials.

Anisotropic dielectric tensors of uniaxial van der Waals (vdW) materials are difficult to investigate at infrared frequencies. The small dimensions of high-quality exfoliated crystals prevent the use of diffraction-limited spectroscopies. Near-field microscopes coupled to broadband lasers can function as Fourier transform infrared spectrometers with nanometric spatial resolution (nano-FTIR). Although dielectric functions of isotropic materials can be readily extracted from nano-FTIR spectra, the in- and out-of-plane permittivities of anisotropic vdW crystals cannot be easily distinguished. For thin vdW crystals residing on a substrate, nano-FTIR spectroscopy probes a combination of sample and substrate responses. We exploit the information in the screening of substrate resonances by vdW crystals to demonstrate that both the in- and out-of-plane dielectric permittivities are identifiable for realistic spectra. This novel method for the quantitative nanoresolved characterization of optical anisotropy was used to determine the dielectric tensor of a bulk 2H-WSe2 microcrystal in the mid-infrared.