A hybrid MBE-based growth method for large-area synthesis of stacked hexagonal boron nitride/graphene heterostructures.
ABSTRACT: Van der Waals heterostructures combining hexagonal boron nitride (h-BN) and graphene offer many potential advantages, but remain difficult to produce as continuous films over large areas. In particular, the growth of h-BN on graphene has proven to be challenging due to the inertness of the graphene surface. Here we exploit a scalable molecular beam epitaxy based method to allow both the h-BN and graphene to form in a stacked heterostructure in the favorable growth environment provided by a Ni(111) substrate. This involves first saturating a Ni film on MgO(111) with C, growing h-BN on the exposed metal surface, and precipitating the C back to the h-BN/Ni interface to form graphene. The resulting laterally continuous heterostructure is composed of a top layer of few-layer thick h-BN on an intermediate few-layer thick graphene, lying on top of Ni/MgO(111). Examinations by synchrotron-based grazing incidence diffraction, X-ray photoemission spectroscopy, and UV-Raman spectroscopy reveal that while the h-BN is relaxed, the lattice constant of graphene is significantly reduced, likely due to nitrogen doping. These results illustrate a different pathway for the production of h-BN/graphene heterostructures, and open a new perspective for the large-area preparation of heterosystems combining graphene and other 2D or 3D materials.
Project description:Combinations of 2D materials with different physical properties can form heterostructures with modified electrical, mechanical, magnetic, and optical properties. The direct observation of a lateral heterostructure synthesis is reported by epitaxial in-plane graphene growth from the step-edge of hexagonal BN (h-BN) within a scanning transmission electron microscope chamber. Residual hydrocarbon in the chamber is the carbon source. The growth interface between h-BN and graphene is atomically identified as largely N-C bonds. This postgrowth method can form graphene nanoribbons connecting two h-BN domains with different twisting angles, as well as isolated carbon islands with arbitrary shapes embedded in the h-BN layer. The electronic properties of the vertically stacked h-BN/graphene heterostructures are investigated by electron energy-loss spectroscopy (EELS). Low-loss EELS analysis of the dielectric response suggests a robust coupling effect between the graphene and h-BN layers.
Project description:The combination of several materials into heterostructures is a powerful method for controlling material properties. The integration of graphene (G) with hexagonal boron nitride (BN) in particular has been heralded as a way to engineer the graphene band structure and implement spin- and valleytronics in 2D materials. Despite recent efforts, fabrication methods for well-defined G-BN structures on a large scale are still lacking. We report on a new method for producing atomically well-defined G-BN structures on an unprecedented length scale by exploiting the interaction of G and BN edges with a Ni(111) surface as well as each other.
Project description:The understanding of interactions between electrons and phonons in atomically thin heterostructures is crucial for the engineering of novel two-dimensional devices. Electron-phonon (el-ph) interactions in layered materials can occur involving electrons in the same layer or in different layers. Here we report on the possibility of distinguishing intralayer and interlayer el-ph interactions in samples of twisted bilayer graphene and of probing the intralayer process in graphene/h-BN by using Raman spectroscopy. In the intralayer process, the el-ph scattering occurs in a single graphene layer and the other layer (graphene or h-BN) imposes a periodic potential that backscatters the excited electron, whereas for the interlayer process the el-ph scattering occurs between states in the Dirac cones of adjacent graphene layers. Our methodology of using Raman spectroscopy to probe different types of el-ph interactions can be extended to study any kind of graphene-based heterostructure.
Project description:Graphene/hexagonal boron nitride (h-BN) monolayer in-plane heterostructure offers a novel material platform for both fundamental research and device applications. To obtain such a heterostructure in high quality via controllable synthetic approaches is still challenging. In this work, in-plane epitaxy of graphene/h-BN heterostructure is demonstrated on Cu-Ni substrates. The introduction of nickel to copper substrate not only enhances the capability of decomposing polyaminoborane residues but also promotes graphene growth via isothermal segregation. On the alloy surface partially covered by h-BN, graphene is found to nucleate at the corners of the as-formed h-BN grains, and the high growth rate for graphene minimizes the damage of graphene-growth process on h-BN lattice. As a result, high-quality graphene/h-BN in-plane heterostructure with epitaxial relationship can be formed, which is supported by extensive characterizations. Photodetector device applications are demonstrated based on the in-plane heterostructure. The success will have important impact on future research and applications based on this unique material platform.
Project description:Two-dimensional (2D) layered materials receive a lot of attention because of their outstanding intrinsic properties and wide applications. In this work, the structural, electronic and magnetic properties of nickel hydroxides (Ni(OH)2) and nitrides XN (X = B, Al, and Ga) heterostructures are studied by first-principles calculations. The results show that the pristine monolayer Ni(OH)2 owns no macro magnetism with antiferromagnetic (AFM) coupling between two nearest Ni atoms, the electronic structure can be modulated through the heterostructures. The Ni(OH)2-GaN and Ni(OH)2-AlN heterostructures retain the AFM coupling, while Ni(OH)2-BN heterostructure have a larger magnetic moment with ferromagnetic (FM) coupling. The complete electron-hole separation is found in the Ni(OH)2-GaN heterostructure. The tunable electronic and magnetic properties of the Ni(OH)2-XN heterostructures open a new door to design the spintronic devices in the 2D stacked nanostructures.
Project description:The thermoelectric voltage generated at an atomically abrupt interface has not been studied exclusively because of the lack of established measurement tools and techniques. Atomically thin 2D materials provide an excellent platform for studying the thermoelectric transport at these interfaces. Here, we report a novel technique and device structure to probe the thermoelectric transport across Au/h-BN/graphene heterostructures. An indium tin oxide (ITO) transparent electrical heater is patterned on top of this heterostructure, enabling Raman spectroscopy and thermometry to be obtained from the graphene top electrode in situ under device operating conditions. Here, an AC voltage V(?) is applied to the ITO heater and the thermoelectric voltage across the Au/h-BN/graphene heterostructure is measured at 2? using a lock-in amplifier. We report the Seebeck coefficient for our thermoelectric structure to be -215 ?V/K. The Au/graphene/h-BN heterostructures enable us to explore thermoelectric and thermal transport on nanometer length scales in a regime of extremely short length scales. The thermoelectric voltage generated at the graphene/h-BN interface is due to thermionic emission rather than bulk diffusive transport. As such, this should be thought of as an interfacial Seebeck coefficient rather than a Seebeck coefficient of the constituent materials.
Project description:In-plane and vertically stacked heterostructures of graphene and hexagonal boron nitride (h-BN-G and G/h-BN, respectively) are both recent focuses of graphene research. However, targeted synthesis of either heterostructure remains a challenge. Here, via chemical vapour deposition and using benzoic acid precursor, we have achieved the selective growth of h-BN-G and G/h-BN through a temperature-triggered switching reaction. The perfect in-plane h-BN-G is characterized by scanning tunnelling microscopy (STM), showing atomically patched graphene and h-BN with typical zigzag edges. In contrast, the vertical alignment of G/h-BN is confirmed by unique lattice-mismatch-induced moiré patterns in high-resolution STM images, and two sets of aligned selected area electron diffraction spots, both suggesting a van der Waals epitaxial mechanism. The present work demonstrates the chemical designability of growth process for controlled synthesis of graphene and h-BN heterostructures. With practical scalability, high uniformity and quality, our approach will promote the development of graphene-based electronics and optoelectronics.
Project description:High-quality large-area graphene/h-BN vertical heterostructures are promising building blocks for many viable applications such as energy harvesting/conversion, electronics and optoelectronics. Here, we successfully grew high-quality large-area graphene/h-BN vertical heterostructures on Pt foils by one-batch low-pressure chemical vapor deposition (LPCVD). We obtained the high quality of about 200-µm-wide graphene/h-BN film having uniform layer thickness. Moreover, the obtained graphene/h-BN heterostructures exhibited field effect mobility of up to 7,200 cm2V-1s-1 at room temperature. These results suggest that such graphene/h-BN heterostructures on recyclable Pt foils grown by LPCVD are promising for high-performance graphene-based electronics.
Project description:Inelastic electron tunneling spectroscopy is a powerful technique for investigating lattice dynamics of nanoscale systems including graphene and small molecules, but establishing a stable tunnel junction is considered as a major hurdle in expanding the scope of tunneling experiments. Hexagonal boron nitride is a pivotal component in two-dimensional Van der Waals heterostructures as a high-quality insulating material due to its large energy gap and chemical-mechanical stability. Here we present planar graphene/h-BN-heterostructure tunneling devices utilizing thin h-BN as a tunneling insulator. With much improved h-BN-tunneling-junction stability, we are able to probe all possible phonon modes of h-BN and graphite/graphene at ? and K high symmetry points by inelastic tunneling spectroscopy. Additionally, we observe that low-frequency out-of-plane vibrations of h-BN and graphene lattices are significantly modified at heterostructure interfaces. Equipped with an external back gate, we can also detect high-order coupling phenomena between phonons and plasmons, demonstrating that h-BN-based tunneling device is a wonderful playground for investigating electron-phonon couplings in low-dimensional systems.
Project description:Hexagonal boron nitride (h-BN) is a promising material for implementation in spintronics due to a large band gap, low spin-orbit coupling, and a small lattice mismatch to graphene and to close-packed surfaces of fcc-Ni(111) and hcp-Co(0001). Epitaxial deposition of h-BN on ferromagnetic metals is aimed at small interface scattering of charge and spin carriers. We report on the controlled growth of h-BN/Ni(111) by means of molecular beam epitaxy (MBE). Structural and electronic properties of this system are investigated using cross-section transmission electron microscopy (TEM) and electron spectroscopies which confirm good agreement with the properties of bulk h-BN. The latter are also corroborated by density functional theory (DFT) calculations, revealing that the first h-BN layer at the interface to Ni is metallic. Our investigations demonstrate that MBE is a promising, versatile alternative to both the exfoliation approach and chemical vapour deposition of h-BN.