Two-dimensional Van Der Waals Materials Research Articles

Graphene-integrated microring cavity for electronically controlled molecular fingerprinting

Microring cavities supporting whispering-gallery modes (WGMs) have an exceptionally high quality factor (Q) and a small mode volume, greatly improving the interaction between light and matter, which has attracted great attention in various microscale/nanoscale photonic devices and potential applications. Recently, two-dimensional van der Waals (vdW) materials such as graphene have emerged as a potential platform for next-generation biosensing by enabling the confinement of light fields at the nanoscale. Here, we propose what we believe to be a novel approach to achieve molecular fingerprint retrieval by integrating graphene into a microring cavity and conducting numerical simulations using the finite-difference time-domain (FDTD) method. The hybrid cavity exhibits high-quality WGMs with a high Q factor of up to 800. Moreover, the resonant wavelength can be electronically controlled through modulation of graphene’s Fermi level, enabling coverage of the entire free spectral range at infrared frequencies. By depositing a thin layer of biomolecular material (e.g., CBP) onto the surface of our hybrid cavity, we are able to accurately read out the absorption spectrum at multiple spectral points, thereby achieving broadband fingerprint retrieval for the targeted biomolecule. Our results pave the way for highly sensitive, chip-integrated, miniaturized, and electrically modulated infrared spectroscopy biosensing.

Superstructure of Fe5-xGeTe2 Determined by Te K-Edge Extended X-ray Absorption Fine Structure and Te Kα X-ray Fluorescence Holography.

The local structure of the two-dimensional van der Waals material, Fe5-xGeTe2, which exhibits unique structural/magnetic phase transitions, was investigated by Te K-edge extended X-ray absorption fine structure (EXAFS) and Te Kα X-ray fluorescence holography (XFH) over a wide temperature range. The formation of a trimer of Te atoms at low temperatures has been fully explored using these methods. An increase in the Te-Fe distance at approximately 150 K was suggested by EXAFS and presumably indicates the formation of a Te trimer. Moreover, XFH displayed clear atomic images of Te atoms. Additionally, the distance between the Te atoms shortened, as confirmed from the atomic images reconstructed from XFH, indicating the formation of a trimer of Te atoms, i.e., a charge-ordered superstructure. Furthermore, Te Kα XFH provided unambiguous atomic images of Fe atoms occupying the Fe1 site; the images were not clearly observed in the Ge Kα XFH that was previously reported because of the low occupancy of Fe and Ge atoms. In this study, EXAFS and XFH clearly showed the local structure around the Te atom; in particular, the formation of Te trimers caused by charge-ordered phase transitions was clearly confirmed. The charge-ordered phase transition is fully discussed based on the structural variation at low temperatures, as established from EXAFS and XFH.

First-Principles Simulation and Materials Screening for Spin-Orbit Torque in 2D van der Waals Heterostructures.

Recent advancements in spin-orbit torque (SOT) technology in two-dimensional van der Waals (2D vdW) materials have not only pushed spintronic devices to their atomic limits but have also unveiled unconventional torques and novel spin-switching mechanisms. The vast diversity of SOT observed in numerous 2D vdW materials necessitates a screening strategy to identify optimal materials for torque device performance. However, such a strategy has yet to be established. To address this critical issue, a combination of density functional theory and non-equilibrium Green's function is employed to calculate the SOT in various 2D vdW bilayer heterostructures. This leads to the discovery of three high SOT systems: WTe2/CrSe2, MoTe2/VS2, and NbSe2/CrSe2. Furthermore, a figure of merit that allows for rapid and efficient estimation of SOT is proposed, enabling high-throughput screening of optimal materials and devices for SOT applications in the future.

Electrochemical Generation of Te Vacancy Pairs in PtTe for Efficient Hydrogen Evolution.

Two-dimensional (2D) van der Waals materials are increasingly seen as potential catalysts due to their unique structures and unmatched properties. However, achieving precise synthesis of these remarkable materials and regulating their atomic and electronic structures at the most fundamental level to enhance their catalytic performance remain a significant challenge. In this study, we synthesized single-crystal bulk PtTe crystals via chemical vapor transport and subsequently produced atomically thin, large PtTe nanosheets (NSs) through electrochemical cathode intercalation. These NSs are characterized by a significant presence of Te vacancy pairs, leading to undercoordinated Pt atoms on their basal planes. Experimental and theoretical studies together reveal that Te vacancy pairs effectively optimize and enhance the electronic properties (such as charge distribution, density of states near the Fermi level, and d-band center) of the resultant undercoordinated Pt atoms. This optimization results in a significantly higher percentage of dangling O-H water, a decreased energy barrier for water dissociation, and an increased binding affinity of these Pt atoms to active hydrogen intermediates. Consequently, PtTe NSs featuring exposed and undercoordinated Pt atoms demonstrate outstanding electrocatalytic activity in hydrogen evolution reactions, significantly surpassing the performance of standard commercial Pt/C catalysts.

Proximity-Induced Exchange Interaction: A New Pathway for Quantum Sensing Using Spin Centers in Hexagonal Boron Nitride.

Defects in hexagonal boron nitride (hBN), a two-dimensional van der Waals material, have attracted a great deal of interest because of its potential in various quantum applications. Due to hBN's two-dimensional nature, the spin center in hBN can be engineered in the proximity of the target material, providing advantages over its three-dimensional counterparts, such as the nitrogen-vacancy center in diamond. Here we propose a novel quantum sensing protocol driven by exchange interaction between the spin center in hBN and the underlying magnetic substrate induced by the magnetic proximity effect. By first-principles calculation, we demonstrate that the induced exchange interaction dominates over the dipole-dipole interaction by orders of magnitude when in the proximity. The interaction remains antiferromagnetic across all stacking configurations between the spin center in hBN and the target van der Waals magnets. Additionally, we explored the scaling behavior of the exchange field as a function of the spatial separation between the spin center and the targets.

Focusing of mid-infrared polaritons through patterned graphene on van der Waals crystals

Abstract Manipulating the propagation of mid-infrared (mid-IR) light is crucial for optical imaging, biosensing, photocatalysis, and guiding photonic circuits. Artificially engineered metamaterials were introduced to comprehensively control optical waves. However, fabrication challenges and optical losses have impeded the progress. Fortunately, two-dimensional van der Waals (vdW) materials are alternatives because of their inherent optical properties, such as hyperbolic behavior, high confinement, low loss, and atomic-scale thickness. In this research, we conducted theoretical and numerical investigations on the α-phase molybdenum trioxide, a biaxial vdW material, with patterned graphene to assess the potential of the tunable focusing of mid-IR light. Our proposed method directly alters the path of excited light to focus mid-IR light by negative refraction. Further, the patterned graphene in our design offers enhanced focusing characteristics, featuring a significantly reduced waist diameter with 1/92 of the free-space wavelength, an enhanced beam quality without pronounced field ripples, and a fivefold increase in field intensity. Moreover, our approach significantly preserves the waist diameter of the focused beam while facilitating directional steering. Thus, the focused beam can propagate in a canalized manner toward the desired direction. These advancements lay the foundation for promising applications in planar photonics.

Contrast-enhanced phase-resolved second harmonic generation microscopy.

The characterization of inverted structures (crystallographic, ferroelectric, or magnetic domains) is crucial in the development and application of novel multi-state devices. However, determining these inverted structures needs a sensitive probe capable of revealing their phase correlation. Here a contrast-enhanced phase-resolved second harmonic generation (SHG) microscopy is presented, which utilizes a phase-tunable Soleil-Babinet compensator and the interference between the SHG fields from the inverted structures and a homogeneous reference. By this means, such inverted structures are correlated through the π-phase difference of SHG, and the phase difference is ultimately converted into the intensity contrast. As a demonstration, we have applied this microscopy in two scenarios to determine the inverted crystallographic domains in two-dimensional van der Waals material MoS2. Our method is particularly suitable for applying in vacuum and cryogenic environments while providing optical diffraction-limited resolution and arbitrarily adjustable contrast. Without loss of generality, this contrast-enhanced phase-resolved SHG microscopy can also be used to resolve other non-centrosymmetric inverted structures, e.g. ferroelectric, magnetic, or multiferroic phases.

Tunable magnetic confinement effect in a magnetic superlattice of graphene

Two-dimensional van der Waals materials such as graphene present an opportunity for band structure engineering using custom superlattice potentials. In this study, we demonstrate how self-assemblies of magnetic iron-oxide (Fe3O4) nanospheres stacked on monolayer graphene generate a proximity-induced magnetic superlattice in graphene and modify its band structure. Interactions between the nanospheres and the graphene layer generate superlattice Dirac points in addition to a gapped energy spectrum near the K and K′ valleys, resulting in magnetic confinement of quasiparticles around the nanospheres. This is evidenced by gate-dependent resistance oscillations, observed in our low temperature transport measurements, and confirmed by self-consistent tight binding calculations. Furthermore, we show that an external magnetic field can tune the magnetic superlattice potential created by the nanospheres, and thus the transport characteristics of the system. This technique for magnetic-field-tuned band structure engineering using magnetic nanostructures can be extended to a broader class of 2D van der Waals and topological materials.

Interfacial Modulation of Spin-Orbit Torques Induced by Two-Dimensional van der Waals Material ZrSe3.

Two-dimensional van der Waals (2D vdW) materials are widely used in spin-orbit torque (SOT) devices. Recent studies have demonstrated the low crystal symmetry and large spin Hall conductivity of 2D vdW ZrSe3, indicating its potential applications in low-power SOT devices. Here, we study the interfacial contribution of SOTs and current-induced magnetization switching in the ZrSe3/Py (Ni80Fe20) and ZrSe3/Cu/Py heterostructures. SOT efficiencies of samples are detected by the spin-torque ferromagnetic resonance (ST-FMR), and out-of-plane damping-like torque (τB) is observed. The ratio between τB and the field-like torque (τA) decreases from 0.175 to 0.138 when inserting 1 nm Cu at the interface and then drops to 0.001 when the thickness of Cu intercalation is 2 nm, indicating that Cu intercalation inhibits the τB component of SOT. Moreover, the SOT efficiency is increased from 3.05 to 5.21, which may be attributed to the Cu intercalation being beneficial to improve the interface between Py and ZrSe3. Theoretical calculation has shown that the Cu spacer can change the conductivity of ZrSe3 from semiconductor to conductor, thereby decreasing the Schottky barrier and increasing the transmission efficiency of the spin current. Furthermore, magneto-optical Kerr effect (MOKE) microscopy is employed to verify the current-driven magnetization switching in these structures. In comparison to the ZrSe3/Py bilayer, the critical current density of ZrSe3/Cu/Py is reduced when inserting 1 nm Cu, demonstrating the higher SOT efficiency and lower power consumption in ZrSe3/Cu/Py structures.

Direct visualization of stacking-selective self-intercalation in epitaxial Nb1+xSe2 films

Two-dimensional (2D) van der Waals (vdW) materials offer rich tuning opportunities generated by different stacking configurations or by introducing intercalants into the vdW gaps. Current knowledge of the interplay between stacking polytypes and intercalation often relies on macroscopically averaged probes, which fail to pinpoint the exact atomic position and chemical state of the intercalants in real space. Here, by using atomic-resolution electron energy-loss spectroscopy in a scanning transmission electron microscope, we visualize a stacking-selective self-intercalation phenomenon in thin films of the transition-metal dichalcogenide (TMDC) Nb1+xSe2. We observe robust contrasts between 180°-stacked layers with large amounts of Nb intercalants inside their vdW gaps and 0°-stacked layers with little detectable intercalants inside their vdW gaps, coexisting on the atomic scale. First-principles calculations suggest that the films lie at the boundary of a phase transition from 0° to 180° stacking when the intercalant concentration x exceeds ~0.25, which we could attain in our films due to specific kinetic pathways. Our results offer not only renewed mechanistic insights into stacking and intercalation, but also open up prospects for engineering the functionality of TMDCs via stacking-selective self-intercalation.

Realization of low potential barrier in MoS2/rGO heterojunction with enhanced electrical conductivity for thin film thermoelectric applications

Two-dimensional (2D) van der Waals materials in-plane anisotropy, caused by a low-symmetric lattice structure, has considerably increased their applications, particularly in thermoelectric. MoS2 and MoS2/reduced graphene oxide (rGO) thin films were grown on SiO2/Si substrate by atmospheric chemical vapor deposition technique to study the thermoelectric performance. Few layered MoS2 was confirmed by the vibrational analysis and the composition elements are confirmed by the x-ray photoelectron spectroscopy technique. The continuous grains lead to reduced phonon life time in A1g and low activation energy assists to enhance the electrical property. The MoS2/rGO has achieved the highest σ of 22 622 S m−1 at 315 K due to an electron-rich cloud around the electrons in S atoms near the adjacent layer of rGO.

Magnetism of MoS2 bilayers with intercalated and surface adsorbed Fe

Magnetic thin films composed of two-dimensional van der Waals materials will play an important role in future spintronics devices. Recently, Tuli et al. performed in-situ MOKE measurements of Fe deposited on an MoS2 substrate and found that a magnetic dead layer (MDL) exists up to approximately 2 Å (Tuli et al. (2021)). To understand the origin of the MDL, we investigate MoS2 bilayers with intercalated and surface adsorbed Fe using first-principles calculations. The results show that the Fe-intercalated bilayer MoS2 is more stable than the bilayer MoS2 with surface adsorbed Fe. The Fe-intercalated bilayer MoS2 is non-magnetic and behaves as the MDL. The systematic investigation of variation in the inter-layer distance between the intercalated Fe layer and surface of MoS2 layer reveals that the strong hybridization between Fe and S is the origin of the MDL. We also show that further intercalation of Fe makes the film magnetic. The results provide a deep understanding of the MDL in two-dimensional van der Waals magnetic materials.

Heavy fermions vs doped Mott physics in heterogeneous Ta-dichalcogenide bilayers

Controlling and understanding electron correlations in quantum matter is one of the most challenging tasks in materials engineering. In the past years a plethora of new puzzling correlated states have been found by carefully stacking and twisting two-dimensional van der Waals materials of different kind. Unique to these stacked structures is the emergence of correlated phases not foreseeable from the single layers alone. In Ta-dichalcogenide heterostructures made of a good metallic “1H”- and a Mott insulating “1T”-layer, recent reports have evidenced a cross-breed itinerant and localized nature of the electronic excitations, similar to what is typically found in heavy fermion systems. Here, we put forward a new interpretation based on first-principles calculations which indicates a sizeable charge transfer of electrons (0.4-0.6 e) from 1T to 1H layers at an elevated interlayer distance. We accurately quantify the strength of the interlayer hybridization which allows us to unambiguously determine that the system is much closer to a doped Mott insulator than to a heavy fermion scenario. Ta-based heterolayers provide therefore a new ground for quantum-materials engineering in the regime of heavily doped Mott insulators hybridized with metallic states at a van der Waals distance.

Sliding-mediated ferroelectric phase transition in CuInP2S6 under pressure

Interlayer stacking order has recently emerged as a unique degree of freedom to control crystal symmetry and physical properties in two-dimensional van der Waals (vdW) materials and heterostructures. By tuning the layer stacking pattern, symmetry-breaking and electric polarization can be created in otherwise non-polar crystals, whose polarization reversal depends on the interlayer sliding motion. Herein, we demonstrate that in a vdW layered ferroelectric, its existing polarization is closely coupled to the interlayer sliding driven by hydrostatic pressure. Through combined structural, electrical, vibrational characterizations, and theoretical calculations, we clearly map out the structural evolution of CuInP2S6 under pressure. A tendency toward a high polarization state is observed in the low-pressure region, followed by an interlayer-sliding-mediated phase transition from a monoclinic to a trigonal phase. Along the transformation pathway, the displacive-instable Cu ion serves as a pivot point that regulates the interlayer interaction in response to external pressure. The rich phase diagram of CuInP2S6, which is enabled by stacking orders, sheds light on the physics of vdW ferroelectricity and opens an alternative route to tailoring long-range order in vdW layered crystals.

Thickness-Tunable Zoology of Magnetic Spin Textures Observed in Fe5GeTe2.

The family of two-dimensional (2D) van der Waals (vdW) materials provides a playground for tuning structural and magnetic interactions to create a wide variety of spin textures. Of particular interest is the ferromagnetic compound Fe5GeTe2 that we show displays a range of complex spin textures as well as complex crystal structures. Here, using a high-brailliance laboratory X-ray source, we show that the majority (1 × 1) Fe5GeTe2 (FGT5) phase exhibits a structure that was previously considered as being centrosymmetric but rather lacks inversion symmetry. In addition, FGT5 exhibits a minority phase that exhibits a long-range ordered (√3 × √3)-R30° superstructure. This superstructure is highly interesting in that it is innately 2D without any lattice periodicity perpendicular to the vdW layers, and furthermore, the superstructure is a result of ordered Te vacancies in one of the topmost layers of the FGT5 sheets rather than being a result of vertical Fe ordering as earlier suggested. We show, from direct real-space magnetic imaging, evidence for three distinct magnetic ground states in lamellae of FGT5 that are stabilized with increasing lamella thickness, namely, a multidomain state, a stripe phase, and an unusual fractal state. In the stripe phase we also observe unconventional type-I and type-II bubbles where the spin texture in the central region of the bubbles is nonuniform, unlike conventional bubbles. In addition, we find a bobber or a cocoon-like spin texture in thick (∼170 μm) FGT5 that emerges from the fractal state in the presence of a magnetic field. Among all the 2D vdW magnets we have thus demonstrated that FGT5 hosts perhaps the richest variety of magnetic phases that, thereby, make it a highly interesting platform for the subtle tuning of magnetic interactions.

Ferroelectric polarization of graphene/h-BN bilayer of different stacking orders

In recent years, two-dimensional van der Waals materials including graphene and hexagonal boron nitride (h-BN) have attracted extensive interest from researchers of many fields. In this paper, the polarization properties of graphene/h-BN van der Waals heterostructures with different stacking orders are explored by first-principle calculations. Notably, the direction of graphene/h-BN heterostructure polarization can be flipped (from AB stacking to BA stacking) by changing its stacking method. According to differential charge density analysis, the interlayer charge redistribution is the main reason driving the polarization flip. Also, we find that the polarization increases with compression of the layers and tensile strain of the lattice. In addition, we investigated the effect of the twisting angle on the polarization. The results show that polarization flip occurs during interlayer rotation and, interestingly, the magnitude and direction of polarization remain constant over a range of twist angles. The results of this study provide insight into the polarization properties of graphene/h-BN heterostructures, which is important for their potential applications in electronic devices.

Deciphering the ultra-high plasticity in metal monochalcogenides.

The quest for electronic devices that offer flexibility, wearability, durability and high performance has spotlighted two-dimensional (2D) van der Waals materials as potential next-generation semiconductors. Especially noteworthy is indium selenide, which has demonstrated surprising ultra-high plasticity. To deepen our understanding of this unusual plasticity in 2D van der Waals materials and to explore inorganic plastic semiconductors, we have conducted in-depth experimental and theoretical investigations on metal monochalcogenides (MX) and transition metal dichalcogenides (MX2). We have discovered a general plastic deformation mode in MX, which is facilitated by the synergetic effect of phase transitions, interlayer gliding and micro-cracks. This is in contrast to crystals with strong atomic bonding, such as metals and ceramics, where plasticity is primarily driven by dislocations, twinning or grain boundaries. The enhancement of gliding barriers prevents macroscopic fractures through a pinning effect after changes in stacking order. The discovery of ultra-high plasticity and the phase transition mechanism in 2D MX materials holds significant potential for the design and development of high-performance inorganic plastic semiconductors.

Methods and optoelectronic device applications of semiconductor epitaxy assisted by two-dimensional van der Waals materials

ABSTRACT This review summarizes research activities on two-dimensional (2D) materials-assisted epitaxy of inorganic semiconductors and their optoelectronic device applications. We presented the overall research related to the growth of epitaxial semiconductor layers on 2D van der Waals materials and discussed various methods to perform controlled growth of semiconductor nanostructures and microstructures on 2D layers. The 2D layers’ benefits in semiconductor technology and their role in non-destructive micro-crystallographic analysis, integration of heterogeneous semiconductor devices, and the fabrication of detachable semiconductor devices. This is followed by an in-depth discussion on 2D materials-assisted growth and non-destructive transfer of random and regular semiconductor arrays and their applications in free-standing, flexible, individually addressable semiconductor optoelectronic devices, including micro display applications. The research covered in this review promotes novel applications of semiconductors grown on 2D materials and exploits ways to synergistically combine their functionalities.

Wafer scale growth of single crystal two-dimensional van der Waals materials.

Two-dimensional (2D) van der Waals (vdW) materials, including graphene, hexagonal boron nitride (hBN), and metal dichalcogenides (MCs), form the basis of modern electronics and optoelectronics due to their unique electronic structure, chemical activity, and mechanical strength. Despite many proof-of-concept demonstrations so far, to fully realize their large-scale practical applications, especially in devices, wafer-scale single crystal atomically thin highly uniform films are indispensable. In this minireview, we present an overview on the strategies and highlight recent significant advances toward the synthesis of wafer-scale single crystal graphene, hBN, and MC 2D thin films. Currently, there are five distinct routes to synthesize wafer-scale single crystal 2D vdW thin films: (i) nucleation-controlled growth by suppressing the nucleation density, (ii) unidirectional alignment of multiple epitaxial nuclei and their seamless coalescence, (iii) self-collimation of randomly oriented grains on a molten metal, (iv) surface diffusion and epitaxial self-planarization and (v) seed-mediated 2D vertical epitaxy. Finally, the challenges that need to be addressed in future studies have also been described.

Evidence of thickness-dependent surface-induced ferroelectricity in few-layer germanium sulfide obtained via scanning tunneling spectroscopy.

The discovery of ferroelectricity in two-dimensional van der Waals materials has sparked enormous interest from the scientific community, due to its possible applications in next-generation nanoelectronic devices, such as random-access memory devices, digital signal processors, and solar cells, among others. In the present study, we used vapor phase deposition to synthesize ultrathin germanium sulfide nano-flakes on a highly oriented pyrolytic graphite substrate. Nanostructures of variable thicknesses were characterized using scanning tunneling microscopy and spectroscopy. Tunneling currents under forward and backward biases were measured as a function of nano-flake thickness. Remarkably, we clearly observed a hysteresis pattern, which we attributed to surface ferroelectric behavior, consistent with the screening conditions of polarization charges. The effect increases as the number of layers is reduced. This experimental result may be directly applicable to miniaturized memory devices, given the two-dimensional nature of this effect.