Interest in layered two dimensional materials, particularly stacked heterostructures of transition metal dichalcogenides, has led to the need for a better understanding of the structural and electronic changes induced by stacking. Here, we investigate the effects of idealized heterostructuring, with periodic commensurate stacking, on the structural, electronic, and vibrational properties, when compared to the counterpart bulk transition metal dichalcogenide. We find that in heterostructures with dissimilar chalcogen species there is a strong compression of the inter-layer spacing, compared to the bulk compounds. This compression of the heterostructure is caused by an increase in the strength of the induced polarization interaction between the layers, but not a full charge transfer. We argue that this effect is real, not due to the imposed commensurability, and should be observable in heterostructures combining different chalcogens. Interestingly, we find that incommensurate stacking of Ti-based dichalcogenides leads to the stabilization of the charge density wave phonon mode, which is unstable in the 1T phase at low temperature. Mixed Ti- and Zr-heterostructures are still unstable, but with a charge density wave or a ferroelectric instability.
We investigate electronic band-structure images in reciprocal space of few layer graphene epitaxially grown on SiC(000-1). In addition to the observation of commensurate rotation angles of the graphene layers, the k-space images recorded near the Fermi edge highlight structures originating from diffraction of the Dirac cones due to the relative rotation of adjacent layers. The 21.9° and 27° rotation angles between two sheets of graphene are responsible for a periodic pattern that can be described with a superlattice unit cells. The superlattice generates replicas of Dirac cones with smaller wa…
Twisted stacked few layer black phosphorus heterostructures were successfully fabricated in this work. Abnormal blue shifts in their Ag1 and Ag2 Raman peaks and unique optical reflections were observed in these samples. The phonon behavior difference can be explained by our density functional theory calculations, which suggest that interlayer coupling has a significant effect in twisted bilayer black phosphorus. According to the calculations, the interlayer interactions are not simply van der Waals interactions. Additional interactions, such as weak valence bonding between the top and bottom f…
We investigate electrical conduction and breakdown behavior of 3D nano-carbon-stacked multilayer graphene (s-MLG) system with complete interlayer decoupling. The s-MLG is prepared by transferring and stacking large-area CVD-grown graphene monolayers, followed by wire patterning and plasma etching. Raman spectroscopy was used to confirm the layer number. The D-band peak indicates low defect level in the samples. Electrical current stressing induced doping is performed to shift the charge-neutrality Dirac point and decrease the graphene/metal contact resistance, improving the overall electrical …
When single-layer h-BN is subjected to a high-energy electron beam, triangular pores with nitrogen edges are formed. Because of the broken sp2 bonds, these pores are known to possess magnetic states. We report on the magnetism and electronic structure of triangular pores as a function of their size. Moreover, in the Bernal-stacked h-BN (AB-h-BN), multilayer pores with parallel edges can be created, which is not possible in the commonly fabricated multilayer AA'-h-BN. Given that these pores can be manufactured in a well-controlled fashion using an electron beam, it is important to understand th…
The anisotropic two-dimensional (2D) van der Waals (vdW) layered materials, with both scientific interest and potential application, have one more dimension to tune the properties than the isotropic 2D materials. The interlayer vdW coupling determines the properties of 2D multi-layer materials by varying stacking orders. As an important representative anisotropic 2D materials, multilayer rhenium disulfide (ReS2) was expected to be random stacking and lack of interlayer coupling. Here, we demonstrate two stable stacking orders (aa and a-b) of N layer (NL, N>1) ReS2 from ultralow-frequency and h…
Multilayer graphene (MLG) grown by chemical vapor deposition (CVD) is a promising material for electronic and optoelectronic devices. Understanding the stacking configuration and interlayer coupling of MLGs is technologically relevant and of importance for the device applications. Here, we reported a kind of twisted MLGs (tMLGs), which are formed by stacking one graphene monolayer on the top of AB-stacked MLG by rotating a certain angle between them. The twist angle of tMLGs are identified by the twist-related modes, R and R'. With increasing the total layer number of N, the observed interlaye…
Raman measurements on monolayer graphene folded back upon itself as an ordered but skew-stacked bilayer (i.e. with interlayer rotation) presents new mechanism for Raman scattering in sp2 carbons that arises in systems that lack coherent AB interlayer stacking. Although the parent monolayer does not exhibit a D-band, the interior of the skewed bilayer produces a strong two-peak Raman feature near 1350 cm-1; one of these peaks is non-dispersive, unlike all previously observed D-band features in sp2 carbons. Within a double-resonant model of Raman scattering, these unusual features are consistent…
Combining MoS$_2$ monolayers to form multilayers allows to access new functionalities. In this work, we examine the correlation between the stacking order and the interlayer coupling of valence states in MoS$_2$ homobilayer samples grown by chemical vapor deposition (CVD) and artificially stacked bilayers from CVD monolayers. We show that hole delocalization over the bilayer is allowed in 2H stacking and results in strong interlayer exciton absorption and also in a larger A-B exciton separation as compared to 3R bilayers, where both holes and electrons are confined to the individual layers. Co…
The optical spectra of vertically stacked MoSe$_2$/WSe$_2$ heterostructures contain additional 'interlayer' excitonic peaks that are absent in the individual monolayer materials and exhibit a significant spatial charge separation in out-of-plane direction. Extending on a previous study, we used a many-body perturbation theory approach to simulate and analyse the excitonic spectra of MoSe$_2$/WSe$_2$ heterobilayers with three stacking orders, considering both momentum-direct and momentum-indirect excitons. We find that the small oscillator strengths and corresponding optical responses of the in…
2D layered materials have recently attracted tremendous interest due to their fascinating properties and potential applications. The interlayer interactions are much weaker than the intralayer bonds, allowing the as-synthesized materials to exhibit different stacking sequences (e.g. ABAB, ABCABC), leading to different physical properties. Here, we show that regardless of the space group of the 2D material, the Raman frequencies of the interlayer shear modes observed under the typical configuration blue shift for AB stacked materials, and red shift for ABC stacked materials, as the number of la…
We demonstrate that surface relaxation, which is insignificant in trilayer graphene, starts to manifest in Bernal-stacked tetralayer graphene. Bernal-stacked few-layer graphene has been investigated by analyzing its Landau level spectra through quantum capacitance measurements. We find that in trilayer graphene, the interlayer interaction parameters were similar to that of graphite. However, in tetralayer graphene, the hopping parameters between the bulk and surface bilayers are quite different. This shows a direct evidence for the surface relaxation phenomena. In spite of the fact that the Va…
Semiconductor heterostructures provide a powerful platform for the engineering of excitons. Here we report the excitonic properties of two-dimensional (2D) heterostructures that consist of monolayer MoS2 and WS2 stacked epitaxially or non-epitaxially in the vertical direction. We find similarly efficient interlayer relaxation and transition of excitons in both the epitaxial and nonepitaxial heterostructures. This is manifested by a two orders of magnitude decrease in the photoluminescence and the appearance of an extra absorption peak at low energy region. The MoS2/WS2 heterostructures show we…
The evolution of electronic structure of graphene nanoribbons (GNRs) as a function of the number of layers stacked together is investigated using \textit{ab initio} density functional theory (DFT) including interlayer van der Waals interactions. Multilayer armchair GNRs (AGNRs), similar to single-layer AGNRs, exhibit three classes of band gaps depending on their width. In zigzag GNRs (ZGNRs), the geometry relaxation resulting from interlayer interactions plays a crucial role in determining the magnetic polarization and the band structure. The antiferromagnetic (AF) interlayer coupling is more …
Two-dimensional layered materials offer the possibility to create artificial vertically stacked structures possessing an additional degree of freedom - $the$ $interlayer$ $twist$. We present a comprehensive optical study of artificially stacked bilayers (BLs) MoS$_2$ encapsulated in hexagonal BN with interlayer twist angle ranging from 0 to 60 degrees using Raman scattering and photoluminescence spectroscopies. It is found that the strength of the interlayer coupling in the studied BLs can be estimated using the energy dependence of indirect emission versus the A$_\textrm{1g}$-E$_\textrm{2g}^1…
Van der Waals (vdW) materials have greatly expanded our design space of heterostructures by allowing individual layers to be stacked at non-equilibrium configurations, for example via control of the twist angle. Such heterostructures not only combine characteristics of the individual building blocks, but can also exhibit emergent physical properties absent in the parent compounds through interlayer interactions. Here we report on a new family of emergent, nanometer-thick, semiconductor 2D ferroelectrics, where the individual constituents are well-studied non-ferroelectric monolayer transition …
The low energy electronic spectra of rotationally faulted graphene bilayers are studied using a long wavelength theory applicable to general commensurate fault angles. Lattice commensuration requires low energy electronic coherence across a fault and preempts massless Dirac behavior near the neutrality point. Sublattice exchange symmetry distinguishes two families of commensurate faults that have distinct low energy spectra which can be interpreted as energy-renormalized forms of the spectra for the limiting Bernal and AA stacked structures. Sublattice-symmetric faults are generically fully ga…
Stacking variations in quasi-2D materials can have an important influence on material properties, such as changing the topology of the band structure. Unfortunately, the weakness of van der Waals interactions makes it difficult to compute the stacking dependence of properties, and even in a material as simple as graphite the stacking energetics remain unclear. Mo$_{1-x}$W$_{x}$Te$_{2}$ is a material in which three differently-stacked phases are conveniently accessible by temperature changes: $1T^{\prime}$, $T^*_d$, and the reported Weyl semimetal phase $T_d$. The transitions proceed via layer …
$α$-graphyne is a two-dimensional sheet of $sp$-$sp^2$ hybridized carbon atoms in a honeycomb lattice. While the geometrical structure is similar to that of graphene, the hybridized triple bonds give rise to electronic structure that is different from that of graphene. Similar to graphene, $α$-graphyne can be stacked in bilayers with two stable configurations, but the different stackings have very different electronic structures: one is predicted to have gapless parabolic bands and the other a tunable band gap which is attractive for applications. In order to realize applications, it is crucia…
Twist-induced magnetic topological phase transition in stacked altermagnetic CrO
School of Physics and Key Laboratory of Quantum State Construction and Manipulation (Ministry of Education), Renmin University of China（中国人民大学物理学院与量子态构建与操控教育部重点实验室）；College of Physics and Optoelectronic Engineering, Shenzhen University（深圳大学物理与光电工程学院）；Hefei National Laboratory（合肥国家实验室）
Interlayer excitons (IXs) possess a much longer lifetime than intralayer excitons due to the spatial separation of the electrons and holes; hence, they have been pursued to create exciton condensates for decades. The recent emergence of two-dimensional (2D) materials, such as transition metal dichalcogenides (TMDs), and of their van der Waals heterostructures (HSs), in which two different 2D materials are layered together, has created new opportunities to study IXs. Here we present the observation of IX gases within two stacked structures consisting of hBN/WSe$_2$/hBN/p: WSe$_2$/hBN. The IX en…
Bilayer borophene has recently attracted much interest due to its outstanding mechanical and electronic properties. The interlayer interactions of these bilayers are reported differently in theoretical and experimental studies. Herein, we design and investigate bilayer beta12-borophene, by first-principles calculations. Our results show that the interlayer distance of the relaxed AA-stacked bilayer is about 2.5 A, suggesting a van der Waals (vdW) interlayer interaction. However, this is not supported by previous experiments, therefore by constraining the interlayer distance, we propose a prefe…
Two-dimensional (2D) materials, such as graphene1, boron nitride2, and transition metal dichalcogenides (TMDs)3-5, have sparked wide interest in both device physics and technological applications at the atomic monolayer limit. These 2D monolayers can be stacked together with precise control to form novel van der Waals heterostructures for new functionalities2,6-9. One highly coveted but yet to be realized heterostructure is that of differing monolayer TMDs with type II band alignment10-12. Their application potential hinges on the fabrication, understanding, and control of bonded monolayers, w…
We propose the nano-scale displacement sensor with high resolution for weak-force systems could be realized based on vertical stacked two-dimensional (2D) atomic corrugated layer materials bound through Van der Waals (VdW) interaction. Using first-principles calculations, we found the electronic structure of bi-layer blue phosphorus (BLBP) varies appreciably to both the lateral and vertical interlayer displacement. The variation of electronic structure due to the lateral displacement is attributed to the changing of the interlayer distance dz led by atomic layer corrugation, which is in a unif…
A major theoretical challenge of studying twisted transition metal dichalcogenide (TMD) bilayers is that the unit cell of such structures is very large and therefore difficult to address using first-principles methods. However, twisted TMD bilayers form moiré patterns, which consist of regions of commensurate stacking, either smoothly interpolated into one another or separated by sharp domain walls. In this paper, we study twisted TMD bilayers by studying the properties of the constituent commensurate structures. Using density functional theory (DFT), we compute band structures for commensurat…
Interlayer interactions perturb the electronic structure of two-dimensional materials and lead to new physical phenomena, such as van Hove singularities and Hofstadter's butterfly pattern. Silicene, the recently discovered two-dimensional form of silicon, is quite unique, in that silicon atoms adopt competing <i>sp</i><sup>2</sup> and <i>sp</i><sup>3</sup> hybridization states leading to a low-buckled structure promising relatively strong interlayer interaction. In multilayer silicene, the stacking order provides an important yet rarely explored degree of freedom for tuning its electronic stru…
Since the strong interlayer interaction of AB-stacked graphene in bulk form degrades the superior property of single-layer graphene, formation of randomly stacked graphene is required to apply the high performances of graphene to macroscopic devices. However, conventional methods to obtain bulk-scale graphene suffer from a low crystallinity and/or the formation of a thermodynamically stable AB-stacked structure. This study develops a novel approach to produce bulk-scale graphene with a high crystallinity and high fractions of random stacking by utilizing the porous morphology of a graphene oxi…
Interlayer electronic coupling in two-dimensional (2D) materials enables tunable and emergent properties by stacking engineering. However, it also brings significant evolution of electronic structures and attenuation of excitonic effects in 2D semiconductors as exemplified by quickly degrading excitonic photoluminescence and optical nonlinearities in transition metal dichalcogenides when monolayers are stacked into van der Waals structures. Here we report a novel van der Waals crystal, niobium oxide dichloride, featuring a vanishing interlayer electronic coupling and scalable second harmonic g…
The existence of strong trigonal warping around the K point for the low energy electronic states in multilayer (N$\geq$2) graphene films and graphite is well established. It is responsible for phenomena such as Lifshitz transitions and anisotropic ballistic transport. The absolute orientation of the trigonal warping with respect to the center of the Brillouin zone is however not agreed upon. Here, we use quasiparticle scattering experiments on a gated bilayer graphene/hexagonal boron nitride heterostructure to settle this disagreement. We compare Fourier transforms of scattering interference m…
Direct, tunable coupling between individually assembled graphene layers is a next step towards designer two-dimensional (2D) crystal systems, with relevance for fundamental studies and technological applications. Here we describe the fabrication and characterization of large-area (> cm^2), coupled bilayer graphene on SiO2/Si substrates. Stacking two graphene films leads to direct electronic interactions between layers, where the resulting film properties are determined by the local twist angle. Polycrystalline bilayer films have a "stained-glass window" appearance explained by the emergence of…
Vertically stacked van der Waals heterostructures constitute a promising platform for providing tailored band alignment with enhanced excitonic systems. Here we report observations of neutral and charged interlayer excitons in trilayer WSe2-MoSe2-WSe2 van der Waals heterostructures and their dynamics. The addition of a WSe2 layer in the trilayer leads to significantly higher photoluminescence quantum yields and tunable spectral resonance compared to its bilayer heterostructures at cryogenic temperatures. The observed enhancement in the photoluminescence quantum yield is due to significantly la…
We investigate the magnetic proximity effect in van der Waals heterostructure formed by a monolayer semiconductor stacked on a 2D ferromagnet, where the lattice mismatch and twisting between the layers typically lead to the formation of moiré pattern. We find that the magnetic proximity effect arising from the spin dependent interlayer coupling depends sensitively on the interlayer atomic registry. Consequently, in the moiré pattern, the spatial variation of the atomic registry leads to a lateral modulation of magnetic proximity field. Such moiré modulated magnetic proximity effect manifests a…
Using molecular dynamics simulations, we investigated an integrated bio-nano interface consisting of a \b{eta}-sheet protein stacked onto graphene. We found that the stacking assembly of the model protein on graphene could be controlled by water molecules. The interlayer water filled within interstices of the bio-nano interface could suppress the molecular vibration of surface groups on protein, and could impair the CH...π interaction driving the attraction of the protein and graphene. The intermolecular coupling of interlayer water would be relaxed by the relative motion of protein upon graph…
Electronic properties of quantum dots (QDs) depend sensitively on their parent materials. Therefore, confined electronic states in graphene QDs (GQDs) of monolayer and Bernal-stacked bilayer graphene are quite different. Twisted bilayer graphene (TBG) is distinct from monolayer and Bernal-stacked bilayer graphene because of the new degree of freedom: twist angle. In the past few years, numerous efforts have been made to realize the GQDs of monolayer and Bernal-stacked bilayer graphene and achieved great success. Thus far, however, strategies for realizing GQDs of TBG have been elusive. Here, w…
Vertically stacked atomic layers from different layered crystals can be held together by van der Waals forces, which can be used for building novel heterostructures, offering a platform for developing a new generation of atomically thin, transparent and flexible devices. The performance of these devices is critically dependent on the layer thickness and the interlayer electronic coupling, influencing the hybridisation of the electronic states as well as charge and energy transfer between the layers. The electronic coupling is affected by the relative orientation of the layers as well as by the…
Interlayer Coupling Driven Correlated and Charge-Ordered Electronic States in a Transition Metal Dichalcogenide Superlattice
Wuhan University（武汉大学）；Hubei University（湖北大学）；Hunan University（湖南大学）；ShanghaiTech University（上海科技大学）；University of Oxford（牛津大学）；Institute of Physics, Chinese Academy of Science（中国科学院物理研究所）；Nanjing University（南京大学）；Wuhan Institute of Quantum Technology（武汉量子技术研究院）
