Search

Atomically sharp heterojunctions in lateral two-dimensional heterostructures can provide the narrowest one-dimensional functionalities driven by unusual interfacial electronic states. For instance, the highly controlled growth of patchworks of graphene and hexagonal boron nitride (h-BN) would be a potential platform to explore unknown electronic, thermal, spin or optoelectronic property. However, to date, the possible emergence of physical properties and functionalities monitored by the interfaces between metallic graphene and insulating h-BN remains largely unexplored. Here, we demonstrate a blue emitting atomic-resolved heterojunction between graphene and h-BN. Such emission is tentatively attributed to localized energy states formed at the disordered boundaries of h-BN and graphene. The weak blue emission at the heterojunctions in simple in-plane heterostructures of h-BN and graphene can be enhanced by increasing the density of the interface in graphene quantum dots array embedded in the h-BN monolayer. This work suggests that the narrowest, atomically resolved heterojunctions of in-plane two-dimensional heterostructures provides a future playground for optoelectronics., This work was supported by the research funds (NRF-2017R1E1A1A01074493 and NRF-2019R1A4A1027934) and the grant (CASE-2013M3A6A5073173) from the centre for Advanced Soft Electronics under the Global Frontier Research Program through the National Research Foundation by the Ministry of Science and ICT, Korea. H.S.S. and K.S. thank the A3 foresight program for their collaboration. Y.S., Y.-C.L. and K.S. acknowledge JSPS KAKENHI Grant Numbers JP19K05223, JP18K14119 and JP16H06333, respectively. S.R. acknowledges the European Union’s Horizon 2020 research and innovation programme under Grant Agreement No. 881603 (Graphene Flagship). ICN2 is funded by the CERCA Programme/Generalitat de Catalunya, and is supported by the Severo Ochoa program from Spanish MINECO (Grant No. SEV-2017-0706). J.E.B.-V. acknowledges funding from PAIP Facultad de Química, UNAM (Grant No. 5000-9173).

The proximity effect of physical quantities like catalysis and wettability is a very interesting and fundamental topic to be studied. However, studies on the catalyst proximity-induced hydrogenatio...

Edge contacts between two-dimensional (2D) materials in the in-plane direction can achieve minimal contact area and low contact resistance, producing atomically thin devices with improved performance. Particularly, lateral heterojunctions of metallic graphene and semiconducting transition metal dichalcogenides (TMDs) exhibit small Schottky barrier heights due to graphene's low work-function. However, issues exist with the fabrication of highly transparent and flexible multi-functional devices utilizing lateral heterostructures (HSs) of graphene and TMDs via spatially controlled growth. This review demonstrates the growth and electronic applications of lateral HSs of graphene and TMDs, highlighting key technologies controlling the wafer-scale growth of continuous films for practical applications. It deepens the understanding of the spatially controlled growth of lateral HSs using chemical vapor deposition methods, and also contributes to the applications that depend on the scale-up of all-2D electronics with ultra-high electrical performance.

Plasmonic biosensing has emerged as the most sensitive label-free technique to detect various molecular species in solutions and has already proved crucial in drug discovery, food safety and studies of bio-reactions. This technique relies on surface plasmon resonances in ~50 nm metallic films and the possibility to functionalize the surface of the metal in order to achieve selectivity. At the same time, most metals corrode in bio-solutions, which reduces the quality factor and darkness of plasmonic resonances and thus the sensitivity. Furthermore, functionalization itself might have a detrimental effect on the quality of the surface, also reducing sensitivity. Here we demonstrate that the use of graphene and other layered materials for passivation and functionalization broadens the range of metals which can be used for plasmonic biosensing and increases the sensitivity by 3-4 orders of magnitude, as it guarantees stability of a metal in liquid and preserves the plasmonic resonances under biofunctionalization. We use this approach to detect low molecular weight HT-2 toxins (crucial for food safety), achieving phase sensitivity~0.5 fg/mL, three orders of magnitude higher than previously reported. This proves that layered materials provide a new platform for surface plasmon resonance biosensing, paving the way for compact biosensors for point of care testing.

Summary Hexagonal boron nitride (h-BN) and its heterostructures with graphene are widely investigated van der Waals (vdW) quantum materials for electronics, photonics, sensing, and energy storage/transduction. However, their metal catalyst-based growth and transfer-based heterostructure assembly approaches present impediments to obtaining high-quality and wafer-scale quantum material. Here, we have presented our perspective on the synthetic strategies that involve direct nucleation of h-BN on various dielectric substrates and its heterostructures with graphene. Mechanistic understanding of direct growth of h-BN via bottom-up approaches such as (a) the chemical-interaction guided nucleation on silicon-based dielectrics, (b) surface nitridation and N+ sputtering of h-BN target on sapphire, and (c) epitaxial growth of h-BN on sapphire, among others, are reviewed. Several design methodologies are presented for the direct growth of vertical and lateral vdW heterostructures of h-BN and graphene. These complex 2D heterostructures exhibit various physical phenomena and could potentially have a range of practical applications., Graphical abstract, Nanotechnology fabrication; Materials synthesis; Nanomaterials

Transition to a commensurate state changes the local symmetry periodicity on two-dimensional van der Waals superstructures, evoking distinctive properties far beyond individual layers. We investigate the morphology of moiré superstructures of graphene on hexagonal boron nitride (hBN) with a low twist angle (≈0°) through moiré fringe analyses with dark field transmission electron microscopy. The moiré fringes exhibit local variation, suggesting that the interaction between graphene and hBN depends on the stacking configuration and that local transition to the commensurate state occurs through the reduced crystalline mismatch (that is, by lattice stretching and twisting on the graphene lattices). This moiré superstructure analysis suggests an inventive method for studying the interaction between stacked van der Waals layers and for discerning the altered electronic and optical properties of graphene on hBN superstructures with a low twist angle, even at low magnification.

Despite a rich choice of two-dimensional materials, which exists these days, heterostructures, both vertical (van der Waals) and in-plane, offer an unprecedented control over the properties and functionalities of the resulted structures. Thus, planar heterostructures allow p-n junctions between different two-dimensional semiconductors and graphene nanoribbons with well-defined edges; and vertical heterostructures resulted in the observation of superconductivity in purely carbon-based systems and realisation of vertical tunnelling transistors. Here we demonstrate simultaneous use of in-plane and van der Waals heterostructures to build vertical single electron tunnelling transistors. We grow graphene quantum dots inside the matrix of hexagonal boron nitride, which allows a dramatic reduction of the number of localised states along the perimeter of the quantum dots. The use of hexagonal boron nitride tunnel barriers as contacts to the graphene quantum dots make our transistors reproducible and not dependent on the localised states, opening even larger flexibility when designing future devices.

Hexagonal boron nitride (h-BN) and graphene have emerged as promising materials for proton exchange membranes because of their high proton conductivity and chemical stability. However, the defects and grain boundaries generated during the growth and transfer of two-dimensional materials limit their practical applicability. Here, we report the fabrication of membrane electrode assemblies using large-area single-oriented AA′-stacked trilayer h-BN (3L-BN), which exhibits very few defects during the growth and transfer, as a proton exchange membrane for use in fuel cell systems. The fuel cell based on AA′-stacked 3L-BN showed a H2 permeation current density as low as 2.69 mA cm–2 and an open circuit voltage (OCV) as high as 0.958 V; this performance is much superior to those for cells based on Nafion (3.7 mA cm–2 and 0.942 V, respectively) and single-layer h-BN (10.08 mA cm–2 and 0.894 V, respectively). Furthermore, the fuel cell with the AA′-stacked 3L-BN membrane almost maintained its original performance (...

Heterostructures of hexagonal boron nitride (h-BN) and graphene have attracted a great deal of attention for potential applications in 2D materials. Although several methods have been developed to produce this material through the partial substitution reaction of graphene, the reverse reaction has not been reported. Though the endothermic nature of this reaction might account for the difficulty and previous absence of such a process, we report herein a new chemical route in which the Pt substrate plays a catalytic role. We propose that this reaction proceeds through h-BN hydrogenation; subsequent graphene growth quickly replaces the initially etched region. Importantly, this conversion reaction enables the controlled formation of patterned in-plane graphene/h-BN heterostructures, without needing the commonly employed protecting mask, simply by using a patterned Pt substrate.

The production of holes by electron beam irradiation in hexagonal boron nitride (hBN), which has a lattice similar to that of graphene, is monitored over time using atomic resolution transmission electron microscopy. The holes appear to be initiated by the formation of a vacancy of boron and grow in a manner that retains an overall triangular shape. The hole growth process involves the formation of single chains of B and N atoms and is accompanied by the ejection of atoms and bundles of atoms along the hole edges, as well as atom migration. These observations are compared to density functional theory calculations and molecular dynamics simulations.

Recently there has been interest in two-dimensional graphene-based superstructures, such as twisted bilayer or trilayer graphene or graphene on hexagonal boron nitride, stacked one on top of the other. These superstructures are expected to have electronic and optical properties that depend on even small changes in the twist angles. By structural mapping in the micrometer scale, we demonstrate that superstructures consist of stacking-induced ‘superlattice domains’. The rotational disorder between domains created by the superstructural defects, such as wrinkles, folds and grain boundaries, and guest species intercalated between stacked layers, was analyzed at a resolution of sub-one degree. This comprehensive approach provides crucial structural information on graphene-based superstructures.

Organic field-effect transistors have gained much attention for their potential use in low-cost, large-area, flexible electronics. High-performance organic transistors require a low density of grain boundaries in their organic films and a reduction of charge traps at the semiconductor-dielectric interface for efficient charge transport. In this respect, the role of the dielectric material is crucial because it primarily determines the growth of the film and the interfacial trap density. Here, we demonstrate the use of chemical-vapor-deposited hexagonal boron nitride (CVD h-BN) as a scalable growth template/dielectric for high-performance organic field-effect transistors. The field-effect transistors based on C60 films grown on single-layer CVD h-BN exhibit an average mobility of 1.7 cm^2V^-1s^-1 and a maximum mobility of 2.9 cm^2V^-1s^-1 with on/off ratios of 10^7. The structural and morphology analysis shows that the epitaxial, two-dimensional growth of C60 on CVD h-BN is mainly responsible for the superior charge transport behavior. We believe that CVD h-BN can serve as a growth template for various organic semiconductors, enabling large-area, high-performance flexible electronics.

Along with the explosive interest in graphene research, much attention has been paid to other two-dimensional (2D) materials such as transition metal dichalcogenides (TMDs) and hexagonal boron nitride (h-BN). In particular, the stacking of various 2D materials in the vertical and lateral directions has been studied recently, as novel physicochemical properties are expected that could result in new applications for electronic devices. In this Perspective, recent advances in the stacking of 2D materials are discussed from the point of view of materials chemistry. In particular, methods for stacking of 2D materials (h-BN/graphene, graphene/WS2 (or MoS2)/graphene, etc.), the properties of vertically and laterally stacked 2D materials, and possible applications are discussed. Finally, we discuss important emerging issues to be studied in future.

Hexagonal boron nitride (h-BN) is gaining significant attention as a two-dimensional dielectric material, along with graphene and other such materials. Herein, we demonstrate the growth of highly crystalline, single-layer h-BN on Pt foil through a low-pressure chemical vapor deposition method that allowed h-BN to be grown over a wide area (8 × 25 mm(2)). An electrochemical bubbling-based method was used to transfer the grown h-BN layer from the Pt foil onto an arbitrary substrate. This allowed the Pt foil, which was not consumed during the process, to be recycled repeatedly. The UV-visible absorption spectrum of the single-layer h-BN suggested an optical band gap of 6.06 eV, while a high-resolution transmission electron microscopy image of the same showed the presence of distinct hexagonal arrays of B and N atoms, which were indicative of the highly crystalline nature and single-atom thickness of the h-BN layer. This method of growing single-layer h-BN over large areas was also compatible with use of a sapphire substrate.

Graphene has been functionalized with spiropyran (SP), a well-known photochromic molecule. It has been realized with pyrene-modified SP, which has been adsorbed on graphene by π-π interaction between pyrene and graphene. The field-effect transistor (FET) with SP-functionalized graphene exhibited n-doping effect and interesting optoelectronic behaviors. The Dirac point of graphene in the FET could be controlled by light modulation because spiropyran can be reversibly switched between two different conformations, a neutral form (colorless SP) and a charge-separated form (purple colored merocyanine, MC), on UV and visible light irradiation. The MC form is produced during UV light irradiation, inducing the shift of the Dirac point of graphene toward negative gate voltage. The reverse process back to the neutral SP form occurred under visible light irradiation or in darkness, inducing a shift of the Dirac point toward positive gate voltage. The change of the Dirac point by UV and visible light was reproducibly repeated. SP molecules also improved the conductance change in the FET device. Furthermore, dynamics on conversion from MC to SP on graphene was different from that in solution and solid samples with SP-grafted polymer or that on gold nanoparticles.

Despite a rich choice of two-dimensional materials, which exists these days, heterostructures, both vertical (van der Waals) and in-plane, offer an unprecedented control over the properties and functionalities of the resulted structures. Thus, planar heterostructures allow p-n junctions between different two-dimensional semiconductors and graphene nanoribbons with well-defined edges; and vertical heterostructures resulted in the observation of superconductivity in purely carbon-based systems and realisation of vertical tunnelling transistors. Here we demonstrate simultaneous use of in-plane and van der Waals heterostructures to build vertical single electron tunnelling transistors. We grow graphene quantum dots inside the matrix of hexagonal boron nitride, which allows a dramatic reduction of the number of localised states along the perimeter of the quantum dots. The use of hexagonal boron nitride tunnel barriers as contacts to the graphene quantum dots make our transistors reproducible and not dependent on the localised states, opening even larger flexibility when designing future devices.