Heterostructures involving graphene and bismuth, with their ability to absorb light over a very wide energy range, are of interest for engineering next-generation opto-electronics. Critical to the technological application of such heterostructures is an understanding of the underlying physics governing their properties. Here, using first-principles calculations, we study the interfacial interactions between graphene and bismuth thin-films. Our study reveals non-intuitive phenomena associated with the moiré-physics of these superlattices. We show a preservation of graphene-derived Dirac cones in spite of proximity to a substrate with large spin-orbit coupling, a greater influence of graphene on the electronic structure properties of bismuth, and the surprising presence of a magnetic solution, only slightly higher in energy (by several meV) than the non-magnetic structure, possibly validating experiments. Such subtle and unanticipated phenomena associated with the moiré-physics are expected to play key roles in the practical applications of heterogeneous assemblies of two-dimensional quantum systems.
We report on graphene-like exfoliation of the large-area crystalline films and ribbons of bismuth telluride with the thicknesses of a few atoms. It is demonstrated that bismuth telluride, the most important material for thermoelectric industry, can be mechanically separated into its building blocks -[Te-Bi-Te-Bi-Te]- atomic five-folds with the thickness of ~1 nm and even further - to subunits with smaller thicknesses. The atomically-thin crystals can be structured into suspended crystalline ribbons providing quantum confinement in two dimensions. The quasi two-dimensional (2-D) crystals of bis…
Resonantly-enhanced Raman response in graphene-capped bismuthene on SiC
Universität Würzburg（维尔茨堡大学）；Würzburg-Dresden Cluster of Excellence ctd.qmat, Universität Würzburg（维尔茨堡大学 würtzburg-dresden 卓越集群 ctd.qmat）；Sapienza University of Rome（罗马第一大学）；RWTH Aachen University（亚琛工业大学）；Forschungszentrum Jülich（于利希研究中心）；Institut für Theoretische Physik und Astrophysik, Universität Würzburg（维尔茨堡大学理论与天体物理研究所）；TUD Dresden University of Technology（德累斯顿工业大学）
Note: Bridging Information Science: AB Initio Calculation Vortex of 2D Materials of Bismuthene(Bismuth Molecule) Graphene-Shaped through Kohn-Sham Equations
The geometric and electronic properties of Bi-adsorbed monolayer graphene, enriched by the strong effect of substrate, are investigated by first-principles calculations. The six-layered substrate, corrugated buffer layer, and slightly deformed monolayer graphene are all simulated. Adatom arrangements are thoroughly studied by analyzing the ground-state energies, bismuth adsorption energies, and Bi-Bi interaction energies of different adatom heights, inter-adatom distance, adsorption sites, and hexagonal positions. A hexagonal array of Bi atoms is dominated by the interactions between the buffe…
Graphene/MoS2 heterostructures are formed by combining the nanosheets of graphene and monolayer MoS2. The electronic features of both constituent monolayers are rather well-preserved in the resultant heterostructure due to the weak van der Waals interaction between the layers. However, the proximity of MoS2 induces strong spin orbit coupling effect of strength ~1 meV in graphene, which is nearly three orders of magnitude larger than the intrinsic spin orbit coupling of pristine graphene. This opens a bandgap in graphene and further causes anticrossings of the spin-nondegenerate bands near the …
Kekulé phases are Peierls-like lattice distortions in graphene that are predicted to host novel electronic states beyond graphene (1-8). Although the Kekulé phases are realized in graphene through introducing electron-electron interactions at high magnetic fields (9-11) or adatom superlattices (12-15), it is still an extremely challenge to obtain large-area graphene Kekulé phases in experiment. Here we demonstrate that sample-wide Kekulé distortions in graphene can be stabilized by using transition metal dichalcogenides (TMDs) as substrates and the induced Kekulé orders are quite robust in the…
We investigate band-gap tuning of bilayer graphene between hexagonal boron nitride sheets, by external electric fields. Using density functional theory, we show that the gap is continuously tunable from 0 to 0.2 eV, and is robust to stacking disorder. Moreover, boron nitride sheets do not alter the fundamental response from that of free-standing bilayer graphene, apart from additional screening. The calculations suggest that the graphene-boron nitride heterostructures could provide a viable route to graphene-based electronic devices.
Heterostructures play significant roles in modern semiconductor devices and micro/nanosystems in a plethora of applications in electronics, optoelectronics, and transducers. While state-of-the-art heterostructures often involve stacks of crystalline epi-layers each down to a few nanometers thick, the intriguing limit would be heterto-atomic-layer structures. Here we report the first experimental demonstration of freestanding van der Waals heterostructures and their functional nanomechanical devices. By stacking single-layer (1L) MoS2 on top of suspended single-, bi-, tri- and four-layer (1L to…
Herein, in-situ reduction of bismuth and graphene oxide was performed by a solvothermal method under a nitrogen atmosphere, and the resulting Bi on RGO nanocomposites were used as an anode material for Mg-ion batteries. The nanocomposite of 60% Bi:40% RGO is a beneficial anode material, delivering a discharge capacity as high as 413 and 372 mAh per g at the specific current of 39 mA per g in the 1st and 50th cycles, respectively. In addition, it shows high-rate capability with the discharge capacities of 381, 372, 354, 295, and 238 mAh per g at the specific currents of 53, 100, 200, 500, and 7…
Fast carrier cooling is important for high power graphene based devices. Strongly Coupled Optical Phonons (SCOPs) play a major role in the relaxation of photoexcited carriers in graphene. Heterostructures of graphene and hexagonal boron nitride (hBN) have shown exceptional mobility and high saturation current, which makes them ideal for applications, but the effect of the hBN substrate on carrier cooling mechanisms is not understood. We track the cooling of hot photo-excited carriers in graphene-hBN heterostructures using ultrafast pump-probe spectroscopy. We find that the carriers cool down f…
Van der Waals heterostructures formed by assembling different two-dimensional atomic crystals into stacks can lead to many new phenomena and device functionalities. In particular, graphene/boron-nitride heterostructures have emerged as a very promising system for band engineering of graphene. However, the intrinsic value and origin of the bandgap in such heterostructures remain unresolved. Here we report the observation of an intrinsic bandgap in epitaxial graphene/boron-nitride heterostructures with zero crystallographic alignment angle. Magneto-optical spectroscopy provides a direct probe of…
Commonly materials are classified as either electrical conductors or insulators. The theoretical discovery of topological insulators (TIs) in 2005 has fundamentally challenged this dichotomy. In a TI, spin-orbit interaction generates a non-trivial topology of the electronic band-structure dictating that its bulk is perfectly insulating, while its surface is fully conducting. The first TI candidate material put forward -graphene- is of limited practical use since its weak spin-orbit interactions produce a band-gap of ~0.01K. Recent reinvestigation of Bi2Se3 and Bi2Te3, however, have firmly cate…
We use confocal Raman microscopy and modified vector analysis methods to investigate the nanoscale origin of strain and carrier concentration in exfoliated graphene-hexagonal boron nitride (hBN) heterostructures on silicon dioxide (SiO2). Two types of heterostructures are studied: graphene on SiO2 partially coved by hBN, and graphene fully encapsulated between two hBN flakes. We extend the vector analysis methods to produce spatial maps of the strain and doping variation across the heterostructures. This allows us to visualise and directly quantify the much-speculated effect of the environment…
Among two-dimensional atomic crystals, hexagonal boron nitride (hBN) is one of the most remarkable materials to fabricate heterostructures revealing unusual properties. We perform first-principles calculations to determine whether intercalated metal atoms and vacancies can mediate interfacial coupling and influence the structural and electronic properties of the graphene/hBN heterostructure. Metal impurity atoms (Li, K, Cr, Mn, Co, and Cu) as extrinsic defects between the graphene and hBN sheets produce $n$-doped graphene. We also consider intrinsic vacancy defects and find that a boron monova…
Gate-tunable synthetic antiferromagnetism with nonrelativistic spin splitting in a graphene/MnS/graphene heterostructure
Institute of Informatics, Slovak Academy of Sciences（斯洛伐克科学院信息学研究所）；Faculty of Physics, University of Belgrade（贝尔格莱德大学物理学院）；Institute of Physics, Pavol Jozef Šafárik University in Košice（科希策帕沃尔·约瑟夫·沙法里克大学物理研究所）；Institute of Experimental Physics, Slovak Academy of Sciences（斯洛伐克科学院实验物理研究所）；New Technologies Research Centre, University of West Bohemia（西波希米亚大学新技术研究中心）
Ultrasensitive acoustic graphene plasmons in a graphene-transition metal dichalcogenide heterostructure: strong plasmon-phonon coupling and wavelength sensitivity enhanced by a metal screen
Heterostructures made by stacking different materials on top of each other are expected to exhibit unusual properties and new phenomena. Interface of the heterostructures plays a vital role in determining their properties. Here, we report the observation of a two-dimensional (2D) spinodal interface in graphene-molybdenum carbide (α-Mo2C) heterostructures, which arises from spinodal decomposition occurring at the heterointerface, by using scanning tunneling microscopy. Our experiment demonstrates that the 2D spinodal interface modulates graphene into whispering gallery resonant networks filled …
Using first-principles calculations, we study the structural and electronic properties of the bilayer SnS/graphene, bilayer SnS/bilayer graphene (AA-stacked), bilayer SnS/bilayer graphene (AB-stacked) and monolayer SnS/graphene/monolayer SnS van der Waals (vdW) heterostructures. Electronic properties of all components of the vdW heterostructures are well preserved, which reflects the weakness of the vdW interaction. In the cases of bilayer SnS/graphene and bilayer SnS/bilayer graphene (AA-stacked), an Ohmic contact is formed which can be turned first into p-type and then into n-type Schottky c…
The electronic properties of two-dimensional materials such as graphene are extremely sensitive to their environment, especially the underlying substrate. Planar van der Waals bonded substrates such as hexagonal boron nitride (hBN) have been shown to greatly improve the electrical performance of graphene devices by reducing topographic variations and charge fluctuations compared to amorphous insulating substrates}. Semiconducting transition metal dichalchogenides (TMDs) are another family of van der Waals bonded materials that have recently received interest as alternative substrates to hBN fo…
We reexamine the electronic structure of graphene on SiC substrate by angle-resolved photoemission spectroscopy. We directly observed multiply cloning of Dirac cone, in addition to ones previously attributed to reconstruction. The locations, relative distances and anisotropy of Dirac cone replicas fully agree with the moiré pattern of graphene-SiC heterostructure. Our results provide a straightforward example of moiré potential modulation in engineering electronic structure with Dirac fermions.
In van der Waals heterostructures, the periodic potential from the Moiré superlattice can be used as a control knob to modulate the electronic structure of the constituent materials. Here we present a nanoscale angle-resolved photoemission spectroscopy (Nano-ARPES) study of transferred graphene/h-BN heterostructures with two different stacking angles of 2.4° and 4.3° respectively. Our measurements reveal six replicas of graphene Dirac cones at the superlattice Brillouin zone (SBZ) centers. The size of the SBZ and its relative rotation angle to the graphene BZ are in good agreement with Moiré s…
Here, we examine the influence of surface chemical reactivity toward ambient gases on the performance of nanodevices based on two-dimensional materials "beyond graphene" and novel topological phases of matter. While surface oxidation in ambient conditions was observed for silicene and phosphorene with subsequent reduction of the mobility of charge carriers, nanodevices with active channels of indium selenide, bismuth chalcogenides and transition-metal dichalcogenides are stable in air. However, air-exposed indium selenide suffers of p-type doping due to water decomposition on Se vacancies, whe…
Two-dimensional (2D) antimony (Sb, antimonene) recently attracted interest due to its peculiar electronic properties and its suitability as anode material in next generation batteries. Sb however exhibits a large polymorphic/allotropic structural diversity, which is also influenced by the Sb's support. Thus understanding Sb heterostructure formation is key in 2D Sb integration. Particularly 2D Sb/graphene interfaces are of prime importance as contacts in electronics and electrodes in batteries. We thus study here few-layered 2D Sb/graphene heterostructures by atomic-resolution (scanning) trans…
We use time- and angle-resolved photoemission spectroscopy (tr-ARPES) to investigate ultrafast charge transfer in an epitaxial heterostructure made of monolayer WS$_2$ and graphene. This heterostructure combines the benefits of a direct gap semiconductor with strong spin-orbit coupling and strong light-matter interaction with those of a semimetal hosting massless carriers with extremely high mobility and long spin lifetimes. We find that, after photoexcitation at resonance to the A-exciton in WS$_2$, the photoexcited holes rapidly transfer into the graphene layer while the photoexcited electro…
The role of defects in van der Waals heterostructures made of graphene and hexagonal boron nitride (h-BN) is studied by a combination of ab initio and model calculations. Despite the weak van der Waals interaction between layers, defects residing in h-BN, such as carbon impurities and antisite defects, reveal a hybridization with graphene p$_{\rm z}$ states, leading to midgap state formation. The induced midgap states modify the transport properties of graphene and can be reproduced by means of a simple effective tight-binding model. In contrast to carbon defects, it is found that oxygen defec…
Van der Waals heterostructures consisting of graphene and transition metal dichalcogenides (TMDCs) have recently shown great promise for high-performance optoelectronic applications. However, an in-depth understanding of the critical processes for device operation, namely interfacial charge transfer (CT) and recombination, has so far remained elusive. Here, we investigate these processes in graphene-WS$_2$ heterostructures, by complementarily probing the ultrafast terahertz photoconductivity in graphene and the transient absorption dynamics in WS$_2$ following photoexcitation. We find that CT …
We report on a scanning confocal Raman spectroscopy study investigating the strain-uniformity and the overall strain and doping of high-quality chemical vapour deposited (CVD) graphene-based heterostuctures on a large number of different substrate materials, including hexagonal boron nitride (hBN), transition metal dichalcogenides, silicon, different oxides and nitrides, as well as polymers. By applying a hBN-assisted, contamination free, dry transfer process for CVD graphene, high-quality heterostructures with low doping densities and low strain variations are assembled. The Raman spectra of …
Graphene/hexagonal boron nitride (G/$h$-BN) heterostructures offer an excellent platform for developing nanoelectronic devices and for exploring correlated states in graphene under modulation by a periodic superlattice potential. Here, we report on transport measurements of nearly $0^{\circ}$-twisted G/$h$-BN heterostructures. The heterostructures investigated are prepared by dry transfer and thermally annealing processes and are in the low mobility regime (approximately $3000~\mathrm{cm}^{2}\mathrm{V}^{-1}\mathrm{s}^{-1}$ at 1.9 K). The replica Dirac spectra and Hofstadter butterfly spectra a…
We report a bipolar field effect tunneling transistor that exploits to advantage the low density of states in graphene and its one atomic layer thickness. Our proof-of-concept devices are graphene heterostructures with atomically thin boron nitride acting as a tunnel barrier. They exhibit room temperature switching ratios ~50, a value that can be enhanced further by optimizing the device structure. These devices have potential for high frequency operation and large scale integration.
The design of stacks of layered materials in which adjacent layers interact by van der Waals forces[1] has enabled the combination of various two-dimensional crystals with different electrical, optical and mechanical properties, and the emergence of novel physical phenomena and device functionality[2-8]. Here we report photo-induced doping in van der Waals heterostructures (VDHs) consisting of graphene and boron nitride layers. It enables flexible and repeatable writing and erasing of charge doping in graphene with visible light. We demonstrate that this photo-induced doping maintains the high…
Understanding magnetoresistance, the change in electrical resistance upon an external magnetic field, at the atomic level is of great interest both fundamentally and technologically. Graphene and other two-dimensional layered materials provide an unprecedented opportunity to explore magnetoresistance at its nascent stage of structural formation. Here, we report an extremely large local magnetoresistance of ~ 2,000% at 400 K and a non-local magnetoresistance of > 90,000% in 9 T at 300 K in few-layer graphene/boron-nitride heterostructures. The local magnetoresistance is understood to arise from…
First-principles calculation has been performed to investigate the stability and electronic properties of double-layer graphene heterostructure (DLGH). In this system, two graphene layers are separated by hexagonal boron-nitride (h-BN) layers which work as a insulating barrier. Our results show that the stability of the system is determined by the atomistic configurations between graphene and its adjacent h-BN layer. Among different stacking sequences, Ab-stacking is most stable. Since the inserted h-BN layers modulate the on-site energies for carbon atoms of graphene layers, the electronic st…
Hexagonal boron nitride (BN), one of the very few layered insulators, plays a crucial role in 2D materials research. In particular, BN grown with a high pressure technique has proven to be an excellent substrate material for graphene and related 2D materials, but at the same time very hard to replace. Here we report on a method of growth at atmospheric pressure as a true alternative for producing BN for high quality graphene/BN heterostructures. The process is not only more scalable, but also allows to grow isotopically purified BN crystals. We employ Raman spectroscopy, cathodoluminescence, a…
Integration of two-dimensional (2D) van der Waals (vdWs) materials with non-2D materials to realize mixed-dimensional heterostructures has potential for creating functional devices beyond the reach of existing materials and has long been a pursuit of the material science community. Here we report the patterning of monolayer/bilayer transition metal dichalcogenide (TMD) nanostructures with nanometer-precision, tunable sizes and sites at interfaces of graphene/TMD heterostructures. Our experiments demonstrate that the TMD nanostructures can be created at selected positions of the interface using…
We report the discovery of a temperature induced phase transition between the αand βstructures of antimonene. When antimony is deposited at room temperature on bismuth selenide, it forms domains of α-antimonene having different orientations with respect to the substrate. During a mild annealing, the βphase grows and prevails over the αphase, eventually forming a single domain that perfectly matches the surface lattice structure of bismuth selenide. First principles thermodynamics calculations of this van der Waals heterostructure explain the different temperature-dependent stability of the two…
We report strongly enhanced perpendicular magnetic anisotropy (PMA) of Co films by graphene coating from both first-principles and experiments. Our calculations show that graphene can dramatically boost the surface anisotropy of Co films up to twice the value of its pristine counterpart and can extend the out-of-plane effective anisotropy up to unprecedented thickness of 25~Å. These findings are supported by our experiments on graphene coating on Co films grown on Ir substrate. Furthermore, we report layer-resolved and orbital-hybridization-resolved anisotropy analysis which help understanding…
Assembling different two-dimensional (2D) crystals, covering a very broad range of properties, into van der Waals (vdW) heterostructures enables the unprecedented possibilities for combining the best of different ingredients in one objective material. So far, metallic, semiconducting, and insulating 2D crystals have been used successfully in making functional vdW heterostructures with properties by design. Here, we expand 2D superconducting crystals as a building block of the vdW hererostructures. A one-step growth of large-scale high-quality vdW heterostructures of graphene and 2D superconduc…
The current research in graphene spintronics strives for achieving a long spin lifetime, and efficient spin injection and detection in graphene. In this article, we review how hexagonal boron nitride (hBN) has evolved as a crucial substrate, as an encapsulation layer, and as a tunnel barrier for manipulation and control of spin lifetimes and spin injection/detection polarizations in graphene spin valve devices. First, we give an overview of the challenges due to conventional SiO$_2$ substrate for spin transport in graphene followed by the progress made in hBN based graphene heterostructures. T…
Hexagonal boron nitride (hBN) is a van der Waals semiconductor with a wide bandgap of ~ 5.96 eV. Despite the indirect bandgap characteristics of hBN, charge carriers excited by high energy electrons or photons efficiently emit luminescence at deep-ultraviolet (DUV) frequencies via strong electron-phonon interaction, suggesting potential DUV light emitting device applications. However, electroluminescence from hBN has not been demonstrated at DUV frequencies so far. In this study, we report DUV electroluminescence and photocurrent generation in graphene/hBN/graphene heterostructures at room tem…
Encapsulating graphene in hexagonal Boron Nitride has several advantages: the highest mobilities reported to date are achieved in this way, and precise nanostructuring of graphene becomes feasible through the protective hBN layers. Nevertheless, subtle effects may arise due to the differing lattice constants of graphene and hBN, and due to the twist angle between the graphene and hBN lattices. Here, we use a recently developed model which allows us to perform band structure and magnetotransport calculations of such structures, and show that with a proper account of the moiré physics an excelle…
Graphene/silicon heterostructures have attracted tremendous interest as a new platform for diverse electronic and photonic devices such as barristors, solar cells, optical modulators, and chemical sensors. The studies to date largely focus on junctions between graphene and lightly-doped silicon, where a Schottky barrier is believed to dominate the carrier transport process. Here we report a systematic investigation of carrier transport across the heterojunctions formed between graphene and highly-doped silicon. By varying the silicon doping level and the measurement temperature, we show that t…
Vertical stacking of atomically thin materials offers a large platform for realizing novel properties enabled by proximity effects and moiré patterns. Here we focus on mechanically assembled heterostructures of graphene and ReS$_2$, a van der Waals layered semiconductor. Using scanning tunneling microscopy and spectroscopy (STM/STS) we image the sharp edge between the two materials as well as areas of overlap. Locally resolved topographic images revealed the presence of a striped superpattern originating in the interlayer interactions between graphene's hexagonal structure and the triclinic, l…
Second-order nonlinear optical response allows to detect different properties of the system associated with the inversion symmetry breaking. Here, we use a second harmonic generation effect to investigate the alignment of a graphene/hexagonal Boron Nitride heterostructure. To achieve that, we activate a commensurate-incommensurate phase transition by a thermal annealing of the sample. We find that this structural change in the system can be directly observed through a strong modification of a nonlinear optical signal. This result reveals the potential of a second harmonic generation technique …
Unraveling the Spin-to-Charge Current Conversion Mechanism and Charge Transfer Dynamics at Interface of Graphene/WS$_2$ Heterostructures at Room Temperature
Finding alternative optoelectronic mechanisms that overcome the limitations of conventional semiconductor devices is paramount for detecting and harvesting low-energy photons. A highly promising approach is to drive a current from the thermal energy added to the free-electron bath as a result of light absorption. Successful implementation of this strategy requires a broadband absorber where carriers interact among themselves more strongly than with phonons, as well as energy-selective contacts to extract the excess electronic heat. Here we show that graphene-WSe2-graphene heterostructure devic…
Van der Waals heterostructures are constructed by stacking different atomic layers and can inherit many novel electronic and optical properties from the constituting atomic layers. Mechanical stability is of key importance for the high performance of nano devices based on the van der Waals heterostructure. In particular, buckling instability is a critical mechanical issue for the heterostructure due to its two-dimensional nature. Using graphene/MoS$_2$ heterostructure as an example, the present work demonstrates the relationship between the buckling instability and the inevitable misfit strain…
We describe a tunneling spectroscopy technique in a double bilayer graphene heterostructure where momentum-conserving tunneling between different energy bands serves as an energy filter for the tunneling carriers, and allows a measurement of the quasi-particle state broadening at well defined energies. The broadening increases linearly with the excited state energy with respect to the Fermi level, and is weakly dependent on temperature. In-plane magnetotunneling reveals a high degree of rotational alignment between the graphene bilayers, and an absence of momentum randomizing processes.
Ferroelectric van der Waals heterostructures provide a natural platform to design a variety of electrically controllable devices. In this work, we demonstrate that AB bilayer graphene encapsulated in MoTe$_2$ acts as a valley valve that displays a switchable built-in topological gap, leading to ferroelectrically driven topological channels. Using a combination of ab initio calculations and low energy models, we show that the ferroelectric order of MoTe$_2$ allows the control of the gap opening in bilayer graphene and leads to topological channels between different ferroelectric domains. Moreov…
We investigate a two-dimensional (2D) heterostructure consisting of few-layer direct bandgap ReS2, a thin h-BN layer and a monolayer graphene for application to various electronic devices. Metal-insulator-semiconductor (MIS)-type devices with two-dimensional (2D) van-der-Waals (vdW) heterostructures have recently been studied as important components to realize various multifunctional device applications in analogue and digital electronics. The tunnel diodes of ReS2/h-BN/graphene exhibit light tuneable rectifying behaviours with low ideality factors and nearly temperature independent electrical…
Van der Waals heterostructures made of graphene and transition metal dichalcogenides (TMD) are an emerging platform for opto-electronic, -spintronic and -valleytronic devices that could benefit from (i) strong light-matter interactions and spin-valley locking in TMDs and (ii) exceptional electron and spin transport in graphene. The operation of such devices requires significant valley polarization and valley coherence, ideally up to room temperature. Here, using a comprehensive Mueller polarimetry analysis, we report \textit{artifact-free} room temperature degrees of valley polarization up to …
