Strong Interlayer Coupling Research Articles

Ultrafast Nanoscopy of High-Density Exciton Phases in WSe2.

The density-driven transition of an exciton gas into an electron-hole plasma remains a compelling question in condensed matter physics. In two-dimensional transition metal dichalcogenides, strongly bound excitons can undergo this phase change after transient injection of electron-hole pairs. Unfortunately, unavoidable nanoscale inhomogeneity in these materials has impeded quantitative investigation into this elusive transition. Here, we demonstrate how ultrafast polarization nanoscopy can capture the Mott transition through the density-dependent recombination dynamics of electron-hole pairs within a WSe2 homobilayer. For increasing carrier density, an initial monomolecular recombination of optically dark excitons transitions continuously into a bimolecular recombination of an unbound electron-hole plasma above 7 × 1012 cm-2. We resolve how the Mott transition modulates over nanometer length scales, directly evidencing the strong inhomogeneity in stacked monolayers. Our results demonstrate how ultrafast polarization nanoscopy could unveil the interplay of strong electronic correlations and interlayer coupling within a diverse range of stacked and twisted two-dimensional materials.

Activating and modifying the basal planes of MoS2 for superior NO2 sensing at room temperature

The gas sensing performance of two-dimensional (2D) materials is greatly hindered by their inactive basal planes. In this work, a hierarchical MoS2 material with a 2D-in-3D architecture has been synthesized by a facile hydrothermal method with subsequent high temperature annealing in argon atmosphere and Zn doping for NO2 gas sensing application. High temperature annealing makes MoS2 material generate a large number of S-vacancy defects and resulting in strong interlayer coupling and spin-orbit coupling effects. It is found that the hierarchical MoS2 annealed at 700 and 850 °C exhibited extremely high gas sensing performance at room temperature in terms of sensitivity, response and recovery speeds, selectivity and stability. The introduction of transition metal Zn element further improves the gas sensing performance of the MoS2 material. After Zn doping, the MoS2 annealed at 850 °C reached an unprecedented gas response of 1405% to 100 ppm NO2 with a detection limit of 8.1 ppb. The relevant gas sensing mechanism is discussed in depth. This work opens up a simple and highly efficient way for activating and modifying the basal planes of MoS2 with robust architecture.

Direct Observation of Orbital Driven Strong Interlayer Coupling in Puckered Two-Dimensional PdSe2.

Interlayer coupling between individual unit layers is known to be critical in manipulating the layer-dependent properties of two-dimensional (2D) materials. While recent studies have revealed that several 2D materials with significant degrees of interlayer interaction (such as black phosphorus) show strongly layer-dependent properties, the origin based on the electronic structure is drawing intensive attention along with 2D materials exploration. Here, the direct observation of a highly dispersive single electronic band along the interlayer direction in puckered 2D PdSe2 as an experimental hallmark of strong interlayer couplings is reported. Remarkably large band dispersion along the kz -direction near Fermi level, which is even wider than the in-plane one, is observed by the angle-resolved photoemission spectroscopy measurement. Employing X-ray absorption spectroscopy and density functional theory calculations, it is revealed that the strong interlayer coupling in 2D PdSe2 originates from the unique directional bonding of Pd d orbitals associated with unexpected Pd 4d9 configuration, which consequently plays a decisive role for the strong layer-dependency of the band gap.

Oxidation behavior of layered FenGeTe2 (n = 3, 4, 5) and Cr2Ge2Te6 governed by interlayer coupling.

Layered magnetic materials have recently received tremendous attention due to an attractive combination of functional properties suitable for nanoelectronics and spintronic applications. Enhancing the air stability of the material is a prerequisite for long-term durability of devices. However, the oxidation mechanism of layered magnetic materials is yet to be revealed. Herein we explore the oxidation behavior of monolayer and multilayer FenGeTe2 (n = 3, 4, 5) and Cr2Ge2Te6 using first-principles calculations. The results show that these monolayer systems are prone to be oxidized in ambient air. With increasing thickness, however, multilayer FenGeTe2 exhibits distinct oxidation behavior from its monolayer counterparts, originating from its unexpected strong interlayer coupling characterized by wavefunction overlapping of adjacent Te atoms between FenGeTe2 layers. Moreover, O2 adsorption does not severely deteriorate the magnetism of layered FenGeTe2 and Cr2Ge2Te6. Given the fact that oxidation properties can be altered by interlayer coupling, our work opens a paradigm for obtaining oxidation-resistant layered materials.

Semiconductor-to-metal transition from monolayer to bilayer blue phosphorous induced by extremely strong interlayer coupling: a first-principles study.

Monolayer blue phosphorous has a large band gap of 2.76 eV but counterintuitively the most stable bilayer blue phosphorous has a negative band gap of -0.51 eV. Such a large band gap reduction from just monolayer to bilayer has not been revealed before, the underlying mechanism behind which is important for understanding interlayer interactions. In this work, we reveal the origin of the semiconductor-to-metal transition using first-principles calculations and tight-binding models. We find that the interlayer interactions are extremely strong, which can be attributed to the short layer distance and strong π-like atomic orbital couplings. Therefore, the upshift of the valence band maximum (VBM) from monolayer to bilayer blue-P is so large that the VBM in the bilayer gets higher than the conduction band minimum, leading to a negative band gap and an energy gain. Besides, the interlayer atomic misplacements weaken the couplings of out-of-plane orbitals. Therefore, the energy gain due to the semiconductor-to-metal transition is larger than the energy cost due to interlayer repulsions, thus stabilizing the metallic phase. The large band gap reduction with layer number increasing is expected to exist in other similar layered systems.

GaS:WS2 Heterojunctions for Ultrathin Two-Dimensional Photodetectors with Large Linear Dynamic Range across Broad Wavelengths.

Two-dimensional (2D) photodetectors based on photovoltaic effect or photogating effect can hardly achieve both high photoresponsivity and large linear dynamic range at the same time, which greatly limits many practical applications such as imaging sensors. Here, the conductive-sensitizer strategy, a general design for improving photoresponsivity and linear dynamic range in 2D photodetectors is provided and experimentally demonstrated on vertically stacked bilayer WS2/GaS0.87 under a parallel circuit mode. Owing to successful band alignment engineering, the isotype type-II heterojunction enables efficient charge carrier transfer from WS2, the high-mobility sensitizer, to GaS0.87, the low-mobility channel, under illumination from a broad visible spectrum. The transferred electron charges introduce a reverse electric field which efficiently lowers the band offset between the two materials, facilitating a transition from low-mobility photocarrier transport to high-mobility photocarrier transport with increasing illumination power. We achieved a large linear dynamic range of 73 dB as well as a high and constant photoresponsivity of 13 A/W under green light. X-ray photoelectron spectroscopy, cathodoluminescence, and Kelvin probe force microscopy further identify the key role of defects in monolayer GaS0.87 in engineering the band alignment with monolayer WS2. This work proposes a design route based on band and interface modulation for improving performance of 2D photodetectors and provides deep insights into the important role of strong interlayer coupling in offering heterostructures with desired properties and functions.

Interlayer Interactions in 1D Van der Waals Moiré Superlattices.

Studying two‐dimensional (2D) van der Waals (vdW) moiré superlattices and their interlayer interactions have received surging attention after recent discoveries of many new phases of matter that are highly tunable. Different atomistic registry between layers forming the inner and outer nanotubes can also form one‐dimensional (1D) vdW moiré superlattices. In this review, experimental observations and theoretical perspectives related to interlayer interactions in 1D vdW moiré superlattices are summarized. The discussion focuses on double‐walled carbon nanotubes (DWNTs), a model 1D vdW moiré system, and the authors highlight the new optical features emerging from the non‐trivial strong interlayer coupling effect and the unique physics in 1D DWNTs. Future directions and questions in probing the intriguing physical phenomena in 1D vdW moiré superlattices such as, correlated physics in different 1D moiré systems beyond DWNTs are proposed and discussed.

Solution-Processed Graphene-Nanographene van der Waals Heterostructures for Photodetectors with Efficient and Ultralong Charge Separation.

Sensitization of graphene with inorganic semiconducting nanostructures has been demonstrated as a powerful strategy to boost its optoelectronic performance. However, the limited tunability of optical properties and toxicity of metal cations in the inorganic sensitizers prohibits their widespread applications, and the in-depth understanding of the essential interfacial charge-transfer process within such hybrid systems remains elusive. Here, we design and develop high-quality nanographene (NG) dispersions with a large-scale production using high-shear mixing exfoliation. The physisorption of these NG molecules onto graphene gives rise to the formation of graphene-NG van der Waals heterostructures (VDWHs), characterized by strong interlayer coupling through π-π interactions. As a proof of concept, photodetectors fabricated on the basis of such VDWHs show ultrahigh responsivity up to 4.5 × 107 A/W and a specific detectivity reaching 4.6 × 1013 Jones, being competitive with the highest values obtained for graphene-based photodetectors. The outstanding device characteristics are attributed to the efficient transfer of photogenerated holes from NGs to graphene and the long-lived charge separation at graphene-NG interfaces (beyond 1 ns), as elucidated by ultrafast terahertz (THz) spectroscopy. These results demonstrate the great potential of such graphene-NG VDWHs as prototypical building blocks for high-performance, low-toxicity optoelectronics.

Interlayer polarizability in twisted bilayer graphene quantum dots

Many of the intriguing properties of bilayer graphene (BLG) are related to interlayer electronic coupling. Since this coupling is sensitive to an applied electric field perpendicular to the layers, we develop a strategy for determining interlayer coupling by decomposing the total electric dipole polarizability, which measures the response of electrons to applied fields, into site-specific contributions and consequently the intralayer and interlayer components. The interlayer polarizability is evaluated from field-induced electron density variations computed with a first-principles approach for twisted BLG quantum dots (QDs). Changes in interlayer polarizability dominate the polarizability variation with twist angle. In addition to the well-recognized strong coupling in the Bernal stackings, enhanced coupling is revealed for the structures at small and size-dependent twist angles when AB stacking first appears in the outermost shell of the QD. The values of these magic angles depend on the QD size. This paper not only provides an approach for measuring interlayer coupling strength but also indicates the existence of strong interlayer coupling even at small twist angles, which could be important for understanding the properties of twisted BLG.

Epitaxial growth of monolayer PdTe2 and patterned PtTe2 by direct tellurization of Pd and Pt surfaces

Two-dimensional (2D) palladium ditelluride (PdTe2) and platinum ditelluride (PtTe2) are two Dirac semimetals, which have fascinating quantum properties such as superconductivity, magnetism and topological order and show the promising applications in future nanoelectronics and optoelectronics. However, the synthesis of PdTe2 and PtTe2 monolayers (MLs) is hindered by a strong interlayer coupling and orbital hybridization. In this study, we demonstrate an efficient synthesis of PdTe2 and PtTe2 MLs Large-area and high quality MLs of PdTe2 and patterned PtTe2 were epitaxially grown on the Pd(111) and Pt(111) surfaces by direct telurization in ultra-high vacuum. This was confirmed by x-ray photoelectron spectroscopy, low energy electron diffraction and scanning tunnelling microscopy. PdTe2 ML demonstrated high thermal stability showing no decomposition sign after annealing at 470 °C. A well-ordered (2 × 2) PtTe2 structure with Kagome lattice was observed on Te/Pt(111) surface following annealing at 200 °C in UHV, where the (2 × 2) pattern was formed by Te atom vacancies. PtTe2 multilayer film was prepared as well, and it demonstrated the excitation of the Dirac plasmons as measured by high-resolution electron energy loss spectroscopy. The direct tellurization offers the simple and reliable protocol for the preparation of the ML of PdTe2 and patterned PtTe2, and this opens new opportunities for quantum phenomena research and for practical optoelectronics applications.

Two-triplon excitations of the Kitaev-Heisenberg bilayer

We study the spectrum of a bilayer of Kitaev magnets on the honeycomb lattice, coupled by Heisenberg exchange in the quantum-dimer phase at strong interlayer coupling. Using the perturbative Continuous Unitary transformation (pCUT) we perform series expansion starting from the fully dimerized limit, to evaluate the elementary excitations, reaching up to and focusing on the two-triplon sector. In stark contrast to conventional bilayer quantum magnets, and because of the broken $SU(2)$-invariance, encoded in the intralayer directional compass-exchange, the bilayer Kitaev magnet is shown to exhibit a rich structure of two-triplon scattering-state continua, as well as several collective two-triplon (anti)bound states. Direct physical pictures for the occurrence of the latter are provided and the (anti)bound states are studied versus the stacking type, the spin components, and the exchange parameters. In addition to the two-triplon spectra, we investigate a corresponding experimental probe by evaluating the magnetic Raman-scattering intensity. We find a very strong sensitivity of this intensity on the two-triplon interactions and the scattering geometry, however a signal from the (anti)bound states appears only in very close proximity to the continuum.

Preparation and Research of Monolayer WS2 FETs Encapsulated by h-BN Material.

Functional devices that use vertical van der Waals (vdWs) heterostructure material can effectively combine the properties of single component materials, and the strong interlayer coupling effect can change their electronic and optical properties. According to our research, WS2/h-BN vertical vdWs heterostructure material can be synthesized by chemical vapor deposition (CVD) and wet transfer methods. Monolayer WS2 material and WS2/h-BN vertical vdWs heterostructure material can be tested and characterized using XPS, SEM, EDS, AFM and Raman spectroscopy, which can prove the existence of corresponding materials. When the thickness of the material decreases, the Coulomb scattering amongst two-dimensional (2D) layered materials increases. This is because both the shielding effect and the distance between the channel and the interface layer decrease. FET devices are then fabricated on WS2/h-BN vdWs heterostructure material by the electron beam lithography and evaporation processes. The effects of vdWs epitaxy on electrical transmission when WS2/h-BN vdWs heterostructure material is formed are explored. Finally, the related electrical performance of FET devices is tested and analyzed. Our experimental research provides guidance for the use of electronic devices with vdWs heterostructure material.

Rashba states situated inside the band gap of InTe/PtSe2 heterostructure

The Rashba effect of two-dimensional (2D) materials draws significant attention because this can boost the development of novel spintronic devices. For the purpose of practical applications, the ideal Rashba states should be formed inside the band gap. However, the reports on ideal Rashba states in 2D materials are still scarce. Here, first-principles calculations are utilized to verify the Rashba spin-orbit coupling of the 2D InTe/PtSe2 van der Waals heterostructure. The occurrence of internal electric field leads to Rashba spin splitting at the valence band edge near the Γ point. These Rashba states are entirely located inside the large band gap, which helps to employ them in practical usages like spintronic devices. We also explore the influence of in-plane strains, interlayer coupling, and external electric fields on the Rashba spin splitting. The Rashba coefficients are increased linearly by the tensile strains, while the compressed strains suppress the Rashba spin splitting. The strong interlayer coupling can also promote the Rashba spin splitting. Compared to the strains, the influence of the external electric field on the Rashba effect is not noteworthy. The synchronous change of Rashba coefficients and dipole moments suggests that the internal electric field is a key factor to affect the Rashba spin splitting.

High-Speed Imaging of Second-Harmonic Generation in MoS2 Bilayer under Femtosecond Laser Ablation.

We report an in situ characterization of transition-metal dichalcogenide (TMD) monolayers and twisted bilayers using a high-speed second-harmonic generation (SHG) imaging technique. High-frequency laser modulation and galvano scanning in the SHG imaging enabled a rapid identification of the crystallinity in the TMD, including the orientation and homogeneity with a speed of 1 frame/s. For a twisted bilayer MoS2, we studied the SHG peak intensity and angles as a function of the twist angle under a strong interlayer coupling. In addition, rapid SHG imaging can be used to visualize laser-induced ablation of monolayer and bilayer MoS2 in situ under illumination by a strong femtosecond laser. Importantly, we observed a characteristic threshold behavior; the ablation process occurred for a very short time duration once the preheating condition was reached. We investigated the laser thinning of the bilayer MoS2 with different twist angles. When the twist angle was 0°, the SHG decreased by approximately one-fourth of the initial intensity when one layer was removed. Conversely, when the twist angle was approximately 60° (the SHG intensity was suppressed), the SHG increased abruptly close to that of the nearby monolayer when one layer was removed. Precise layer-by-layer control was possible because of the unique threshold behavior of the laser-induced ablation.

Strong interlayer coupling in two-dimensional PbSe with high thermoelectric performance

It was generally believed that weak van der Waals interactions exist between neighboring layers in the two-dimensional group-IV chalcogenides. Using PbSe as a prototypal example, we find additional strong coupling between the Pb–Pb layers, as evidenced by detailed analysis of the differential charge density plot. The coupling is covalent-like and can be fine-tuned to obviously reduce the phonon thermal conductivity but slightly change the electronic transport of PbSe layer. As a consequence, a maximum ZT value of 2.5 can be realized at 900 K for the p-type system. Our work also offers an effective and feasible design strategy to enhance the thermoelectric performance of similar layered structures.

Ultrathin platinum diselenide synthesis controlling initial growth kinetics: Interfacial reaction depending on thickness and substrate

Platinum diselenide (PtSe2) is an emerging transition-metal dichalcogenide showing both strong interlayer coupling and remarkable electrical properties. Because field-effect transistors (FETs) recently fabricated using PtSe2 films grown by various methods have not shown the high mobilities and on–off ratios compared with exfoliated PtSe2 and predicted by theoretical calculations, the PtSe2 growth mechanism must be better understood to prevent the degradation of electrical properties and improve the electrical performances of PtSe2-based devices. Therefore, molecular beam epitaxy is used in the current study to grow PtSe2 films, and a correlation is demonstrated between the initial PtSe2 growth kinetics and the electrical performances of PtSe2-based devices. X-ray photoelectron spectroscopy and annular dark field–scanning transmission electron microscopy show that metallic Platinum (Pt) is present in the thin PtSe2 films, as explained by the density functional theory calculations comparing Pt–Pt bond with Pt–Se bond. Electrical measurements of the PtSe2-based FETs show that the electrical performances are closely correlated with the initial growth kinetics of the PtSe2 films, indicating that removing Pt (which degrades device performance) is the most important aspect of growing thin PtSe2 films to optimize device performance.

Thermal Gating of Magnon Exchange in Magnetic Multilayers with Antiferromagnetic Spacers.

We observe a strong thermally controlled magnon-mediated interlayer coupling of two ferromagnetic layers via an antiferromagnetic spacer in spin-valve type trilayers. The effect manifests itself as a coherent switching as well as collective resonant precession of the two ferromagnets, which can be controlled by varying temperature and the spacer thickness. We explain the observed behavior as due to a strong hybridization of the ferro- and antiferromagnetic magnon modes in the trilayer at temperatures just below the Néel temperature of the antiferromagnetic spacer.

Electronic structure of 3∘ -twisted bilayer graphene on 4H-SiC(0001)

Interesting electronic properties of a-few-degree-twisted bilayer graphene are caused by the formation of a flat band due to the interlayer interaction and electronic correlation. The authors quantitatively investigated the band structure of wide 3${}^{\mathrm{deg}}$-twisted bilayer graphene with clean interface by angle-resolved photoelectron spectroscopy, and compare the results with those of a band calculation using a recently-developed band unfolding method. The observed band structure indicates strong interlayer coupling that renormalizes the band structure including partial flat band features and gap formation. The observed band structure is in good agreement with the calculated results, indicating the importance of the interlayer coupling for the band renormalization.

Signatures of strong interlayer coupling in γ-InSe revealed by local differential conductivity* *Project supported by the National Natural Science Foundation of China (Grant Nos. 51772087, 11804089, 11574350, 11904094, and 51972106), the Natural Science Foundation of Hunan Province, China (Grant Nos. 2018JJ3025, 2019JJ50034, and 2019JJ50073), the Strategic Priority Research Program of Chinese Academy of Sciences (Grant No. XDB30000000), and the Fundamental

Interlayer coupling in layered semiconductors can significantly affect their optoelectronic properties. However, understanding the mechanisms behind the interlayer coupling at the atomic level is not straightforward. Here, we study modulations of the electronic structure induced by the interlayer coupling in the γ-phase of indium selenide (γ-InSe) using scanning probe techniques. We observe a strong dependence of the energy gap on the sample thickness and a small effective mass along the stacking direction, which are attributed to strong interlayer coupling. In addition, the moiré patterns observed in γ-InSe display a small band-gap variation and nearly constant local differential conductivity along the patterns. This suggests that modulation of the electronic structure induced by the moiré potential is smeared out, indicating the presence of a significant interlayer coupling. Our theoretical calculations confirm that the interlayer coupling in γ-InSe is not only of the van der Waals origin, but also exhibits some degree of hybridization between the layers. Strong interlayer coupling might play an important role in the performance of γ-InSe-based devices.

Enhanced second-order Stark effect in twisted bilayer graphene quantum dots

External electric field and interlayer twist introduce diverse changes in their confined electronic states of bilayer graphene quantum dots. Using a quantum-dot model, the band gaps of twisted bilayer graphene in finite sizes of about 1.4–2.4 nm with varying twist angles are studied in the presence of an electrostatic field perpendicular to the flakes by means of first-principles calculations. The size-dependent gaps are widened by the interlayer twist, but narrowed by the applied field. Their coupling, however, results in an enhanced Stark response in the twisted structures of which the field-induced band-gap variations are about 3–4 times as large as that of the corresponding untwisted structures under the same field strength. The exceptional Stark shifts come from the field-induced asynchronous shifts in their occupied and virtual energy levels, which are further enhanced by strong interlayer coupling at specific twist angles. Moreover, the shift of band gaps with the field strength follows the quadratic Stark response with large second-order shifting coefficients. The enhanced and tunable Stark shift suggests a gateway to the band engineering of bilayer graphene quantum dots by tuning their sizes, twist angles and their coupling with applied field.