2D Memory Selectors with Giant Nonlinearity Enabled by Van der Waals Heterostructures.

The integration of one-selector-one-resistor crossbar arrays requires the selectors featured with high nonlinearity and bipolarity to prevent leakage currents and any crosstalk among distinct cells. However, a selector with sufficient nonlinearity especially in the frame of device miniaturization remains scarce, restricting the advance of high-density storage devices. Herein, a high-performance memory selector is reported by constructing a graphene/hBN/WSe2 heterostructure. Within the temperature range of 300-80 K, the nonlinearity of this selector varies from ≈103 - ≈104 under forward bias, and increases from ≈300 - ≈105 under reverse bias, the highest reported nonlinearity among 2D selectors. This improvement is ascribed to direct tunneling at low bias and Fowler-Nordheim tunneling at high bias. The tunneling current versus voltage curves exhibit excellent bipolarity behavior because of the comparable hole and electron tunneling barriers, and the charge transport polarity can be effectively tuned from N-type or P-type to bipolar by simply changing source-drain bias. In addition, the conceptual memory selector exhibits no sign of deterioration after 70 000 switching cycles, paving the way for assembling 2D selectors into modern memory devices.

Tunable Interband Transitions in Twisted h-BN/Graphene Heterostructures.

In twisted h-BN/graphene heterostructures, the complex electronic properties of the fast-traveling electron gas in graphene are usually considered to be fully revealed. However, the randomly twisted heterostructures may also have unexpected transition behaviors, which may influence the device performance. Here, we study the twist-angle-dependent coupling effects of h-BN/graphene heterostructures using monochromatic electron energy loss spectroscopy. We find that the moiré potentials alter the band structure of graphene, resulting in a redshift of the intralayer transition at the M point, which becomes more pronounced up to 0.22 eV with increasing twist angle. Furthermore, the twisting of the Brillouin zone of h-BN relative to the graphene M point leads to tunable vertical transition energies in the range of 5.1-5.6 eV. Our findings indicate that twist-coupling effects of van der Waals heterostructures should be carefully considered in device fabrications, and the continuously tunable interband transitions through the twist angle can serve as a new degree of freedom to design optoelectrical devices.

Universal epitaxy of non-centrosymmetric two-dimensional single-crystal metal dichalcogenides.

The great challenge for the growth of non-centrosymmetric 2D single crystals is to break the equivalence of antiparallel grains. Even though this pursuit has been partially achieved in boron nitride and transition metal dichalcogenides (TMDs) growth, the key factors that determine the epitaxy of non-centrosymmetric 2D single crystals are still unclear. Here we report a universal methodology for the epitaxy of non-centrosymmetric 2D metal dichalcogenides enabled by accurate time sequence control of the simultaneous formation of grain nuclei and substrate steps. With this methodology, we have demonstrated the epitaxy of unidirectionally aligned MoS2 grains on a, c, m, n, r and v plane Al2O3 as well as MgO and TiO2 substrates. This approach is also applicable to many TMDs, such as WS2, NbS2, MoSe2, WSe2 and NbSe2. This study reveals a robust mechanism for the growth of various 2D single crystals and thus paves the way for their potential applications.

Continuous epitaxy of single-crystal graphite films by isothermal carbon diffusion through nickel.

Multilayer van der Waals (vdW) film materials have attracted extensive interest from the perspective of both fundamental research1-3 and technology4-7. However, the synthesis of large, thick, single-crystal vdW materials remains a great challenge because the lack of out-of-plane chemical bonds weakens the epitaxial relationship between neighbouring layers8-31. Here we report the continuous epitaxial growth of single-crystal graphite films with thickness up to 100,000 layers on high-index, single-crystal nickel (Ni) foils. Our epitaxial graphite films demonstrate high single crystallinity, including an ultra-flat surface, centimetre-size single-crystal domains and a perfect AB-stacking structure. The exfoliated graphene shows excellent physical properties, such as a high thermal conductivity of ~2,880 W m-1 K-1, intrinsic Young's modulus of ~1.0 TPa and low doping density of ~2.2 × 1010 cm-2. The growth of each single-crystal graphene layer is realized by step edge-guided epitaxy on a high-index Ni surface, and continuous growth is enabled by the isothermal dissolution-diffusion-precipitation of carbon atoms driven by a chemical potential gradient between the two Ni surfaces. The isothermal growth enables the layers to grow at optimal conditions, without stacking disorders or stress gradients in the final graphite. Our findings provide a facile and scalable avenue for the synthesis of high-quality, thick vdW films for various applications.

Designed growth of large bilayer graphene with arbitrary twist angles.

The production of large-area twisted bilayer graphene (TBG) with controllable angles is a prerequisite for proceeding with its massive applications. However, most of the prevailing strategies to fabricate twisted bilayers face great challenges, where the transfer methods are easily stuck by interfacial contamination, and direct growth methods lack the flexibility in twist-angle design. Here we develop an effective strategy to grow centimetre-scale TBG with arbitrary twist angles (accuracy, <1.0°). The success in accurate angle control is realized by an angle replication from two prerotated single-crystal Cu(111) foils to form a Cu/TBG/Cu sandwich structure, from which the TBG can be isolated by a custom-developed equipotential surface etching process. The accuracy and consistency of the twist angles are unambiguously illustrated by comprehensive characterization techniques, namely, optical spectroscopy, electron microscopy, photoemission spectroscopy and photocurrent spectroscopy. Our work opens an accessible avenue for the designed growth of large-scale two-dimensional twisted bilayers and thus lays the material foundation for the future applications of twistronics at the integration level.

Visualizing the Anomalous Catalysis in Two-Dimensional Confined Space.

Confined nanospaces provide a new platform to promote catalytic reactions. However, the mechanism of catalytic enhancement in the nanospace still requires insightful exploration due to the lack of direct visualization. Here, we report operando investigations on the etching and growth of graphene in a two-dimensional (2D) confined space between graphene and a Cu substrate. We observed that the graphene layer between the Cu and top graphene layer was surprisingly very active in etching (more than 10 times faster than the etching of the top graphene layer). More strikingly, at a relatively low temperature (∼530 °C), the etched carbon radicals dissociated from the bottom layer, in turn feeding the growth of the top graphene layer with a very high efficiency. Our findings reveal the in situ dynamics of the anomalous confined catalytic processes in 2D confined spaces and thus pave the way for the design of high-efficiency catalysts.

Robust growth of two-dimensional metal dichalcogenides and their alloys by active chalcogen monomer supply.

The precise precursor supply is a precondition for controllable growth of two-dimensional (2D) transition metal dichalcogenides (TMDs). Although great efforts have been devoted to modulating the transition metal supply, few effective methods of chalcogen feeding control were developed. Here we report a strategy of using active chalcogen monomer supply to grow high-quality TMDs in a robust and controllable manner, e.g., MoS2 monolayers perform representative photoluminescent circular helicity of ~92% and electronic mobility of ~42 cm2V-1s-1. Meanwhile, a uniform quaternary TMD alloy with three different anions, i.e., MoS2(1-x-y)Se2xTe2y, was accomplished. Our mechanism study revealed that the active chalcogen monomers can bind and diffuse freely on a TMD surface, which enables the effective nucleation, reaction, vacancy healing and alloy formation during the growth. Our work offers a degree of freedom for the controllable synthesis of 2D compounds and their alloys, benefiting the development of high-end devices with desired 2D materials.

Dual-coupling-guided epitaxial growth of wafer-scale single-crystal WS2 monolayer on vicinal a-plane sapphire.

The growth of wafer-scale single-crystal two-dimensional transition metal dichalcogenides (TMDs) on insulating substrates is critically important for a variety of high-end applications1-4. Although the epitaxial growth of wafer-scale graphene and hexagonal boron nitride on metal surfaces has been reported5-8, these techniques are not applicable for growing TMDs on insulating substrates because of substantial differences in growth kinetics. Thus, despite great efforts9-20, the direct growth of wafer-scale single-crystal TMDs on insulating substrates is yet to be realized. Here we report the successful epitaxial growth of two-inch single-crystal WS2 monolayer films on vicinal a-plane sapphire surfaces. In-depth characterizations and theoretical calculations reveal that the epitaxy is driven by a dual-coupling-guided mechanism, where the sapphire plane-WS2 interaction leads to two preferred antiparallel orientations of the WS2 crystal, and sapphire step edge-WS2 interaction breaks the symmetry of the antiparallel orientations. These two interactions result in the unidirectional alignment of nearly all the WS2 islands. The unidirectional alignment and seamless stitching of WS2 islands are illustrated via multiscale characterization techniques; the high quality of WS2 monolayers is further evidenced by a photoluminescent circular helicity of ~55%, comparable to that of exfoliated WS2 flakes. Our findings offer the opportunity to boost the production of wafer-scale single crystals of a broad range of two-dimensional materials on insulators, paving the way to applications in integrated devices.

Complete structural characterization of single carbon nanotubes by Rayleigh scattering circular dichroism.

Non-invasive, high-throughput spectroscopic techniques can identify chiral indices (n,m) of carbon nanotubes down to the single-tube level1-6. Yet, for complete characterization and to unlock full functionality, the handedness, the structural property associated with mirror symmetry breaking, also needs to be identified accurately and efficiently7-14. So far, optical methods fail in the handedness characterization of single nanotubes because of the extremely weak chiroptical signals (roughly 10-7) compared with the excitation light15,16. Here we demonstrate the complete structure identification of single nanotubes in terms of both chiral indices and handedness by Rayleigh scattering circular dichroism. Our method is based on the background-free feature of Rayleigh scattering collected at an oblique angle, which enhances the nanotube's chiroptical signal by three to four orders of magnitude compared with conventional absorption circular dichroism. We measured a total of 30 single-walled carbon nanotubes including both semiconducting and metallic nanotubes and found that their absolute chiroptical signals show a distinct structure dependence, which can be qualitatively understood through tight-binding calculations. Our strategy enables the exploration of handedness-related functionality of single nanotubes and provides a facile platform for chiral discrimination and chiral device exploration at the level of individual nanomaterials.

Development of in situ optical spectroscopy with high temporal resolution in an aberration-corrected transmission electron microscope.

Exploring the corresponding relation between structural and physical properties of materials at the atomic scale remains the fundamental problem in science. With the development of the aberration-corrected transmission electron microscopy (AC-TEM) and the ultrafast optical spectroscopy technique, sub-angstrom-scale spatial resolution and femtosecond-scale temporal resolution can be achieved, respectively. However, the attempt to combine both their advantages is still a great challenge. Here, we develop in situ optical spectroscopy with high temporal resolution in AC-TEM by utilizing a self-designed and manufactured TEM specimen holder, which has the capacity of sub-angstrom-scale spatial resolution and femtosecond-scale temporal resolution. The key and unique design of our apparatus is the use of the fiber bundle, which enables the delivery of focused pulse beams into TEM and collection of optical response simultaneously. The generated focused spot has a size less than 2 µm and can be scanned in plane with an area larger than 75 × 75 µm2. Most importantly, the positive group-velocity dispersion caused by glass fiber is compensated by a pair of diffraction gratings, thus resulting in the generation of pulse beams with a pulse width of about 300 fs (@ 3 mW) in TEM. The in situ experiment, observing the atomic structure of CdSe/ZnS quantum dots in AC-TEM and obtaining the photoluminescence lifetime (∼4.3 ns) in the meantime, has been realized. Further ultrafast optical spectroscopy with femtosecond-scale temporal resolution could be performed in TEM by utilizing this apparatus.

Optical fibres with embedded two-dimensional materials for ultrahigh nonlinearity.

Nonlinear optical fibres have been employed for a vast number of applications, including optical frequency conversion, ultrafast laser and optical communication1-4. In current manufacturing technologies, nonlinearity is realized by the injection of nonlinear materials into fibres5-7 or the fabrication of microstructured fibres8-10. Both strategies, however, suffer from either low optical nonlinearity or poor design flexibility. Here, we report the direct growth of MoS2, a highly nonlinear two-dimensional material11, onto the internal walls of a SiO2 optical fibre. This growth is realized via a two-step chemical vapour deposition method, where a solid precursor is pre-deposited to guarantee a homogeneous feedstock before achieving uniform two-dimensional material growth along the entire fibre walls. By using the as-fabricated 25-cm-long fibre, both second- and third-harmonic generation could be enhanced by ~300 times compared with monolayer MoS2/silica. Propagation losses remain at ~0.1 dB cm-1 for a wide frequency range. In addition, we demonstrate an all-fibre mode-locked laser (~6 mW output, ~500 fs pulse width and ~41 MHz repetition rate) by integrating the two-dimensional-material-embedded optical fibre as a saturable absorber. Initial tests show that our fabrication strategy is amenable to other transition metal dichalcogenides, making these embedded fibres versatile for several all-fibre nonlinear optics and optoelectronics applications.

Unveiling the Fine Structural Distortion of Atomically Thin Bi2 O2 Se by Third-Harmonic Generation.

Bismuth oxyselenide (Bi2 O2 Se), a new type of 2D material, has recently attracted increased attention due to its robust bandgap, stability under ambient conditions, and ultrahigh electron mobility. In such complex oxides, fine structural distortion tends to play a decisive role in determining the unique physical properties, such as the ferrorotational order, ferroelectricity, and magnetoelasticity. Therefore, an in-depth investigation of the fine structural symmetry of Bi2 O2 Se is necessary to exploit its potential applications. However, conventional techniques are either time consuming or requiring tedious sample treatment. Herein, a noninvasive and high-throughput approach is reported for characterizing the fine structural distortion in 2D centrosymmetric Bi2 O2 Se by polarization-dependent third-harmonic generation (THG). Unprecedentedly, the divergence between the experimental results and the theoretical prediction of the perpendicular component of polarization-dependent THG indicates a fine structural distortion, namely, a <1.4° rotation of the oxygen square in the tetragonal (Bi2 O2 ) layers. This rotation breaks the intrinsic mirror symmetry of 2D Bi2 O2 Se, eventually reducing the symmetry from the D4h to the C4h point group. The results demonstrate that THG is highly sensitive to even fine symmetry variations, thereby showing its potential to uncover hidden phase transitions and interacting polarized sublattices in novel 2D material systems.

Seeded growth of large single-crystal copper foils with high-index facets.

The production of large single-crystal metal foils with various facet indices has long been a pursuit in materials science owing to their potential applications in crystal epitaxy, catalysis, electronics and thermal engineering1-5. For a given metal, there are only three sets of low-index facets ({100}, {110} and {111}). In comparison, high-index facets are in principle infinite and could afford richer surface structures and properties. However, the controlled preparation of single-crystal foils with high-index facets is challenging, because they are neither thermodynamically6,7 nor kinetically3 favourable compared to low-index facets6-18. Here we report a seeded growth technique for building a library of single-crystal copper foils with sizes of about 30 × 20 square centimetres and more than 30 kinds of facet. A mild pre-oxidation of polycrystalline copper foils, followed by annealing in a reducing atmosphere, leads to the growth of high-index copper facets that cover almost the entire foil and have the potential of growing to lengths of several metres. The creation of oxide surface layers on our foils means that surface energy minimization is not a key determinant of facet selection for growth, as is usually the case. Instead, facet selection is dictated randomly by the facet of the largest grain (irrespective of its surface energy), which consumes smaller grains and eliminates grain boundaries. Our high-index foils can be used as seeds for the growth of other Cu foils along either the in-plane or the out-of-plane direction. We show that this technique is also applicable to the growth of high-index single-crystal nickel foils, and we explore the possibility of using our high-index copper foils as substrates for the epitaxial growth of two-dimensional materials. Other applications are expected in selective catalysis, low-impedance electrical conduction and heat dissipation.

Kinetic modulation of graphene growth by fluorine through spatially confined decomposition of metal fluorides.

Two-dimensional materials show a variety of promising properties, and controlling their growth is an important aspect for practical applications. To this end, active species such as hydrogen and oxygen are commonly introduced into reactors to promote the synthesis of two-dimensional materials with specific characteristics. Here, we demonstrate that fluorine can play a crucial role in tuning the growth kinetics of three representative two-dimensional materials (graphene, hexagonal boron nitride and WS2). When growing graphene by chemical vapour deposition on a copper foil, fluorine released from the decomposition of a metal fluoride placed near the copper foil greatly accelerates the growth of the graphene (up to a rate of ~200 µm s-1). Theoretical calculations show that it does so by promoting decomposition of the methane feedstock, which converts the endothermic growth process to an exothermic one. We further show that the presence of fluorine also accelerates the growth of two-dimensional hexagonal boron nitride and WS2.

Epitaxial growth of a 100-square-centimetre single-crystal hexagonal boron nitride monolayer on copper.

The development of two-dimensional (2D) materials has opened up possibilities for their application in electronics, optoelectronics and photovoltaics, because they can provide devices with smaller size, higher speed and additional functionalities compared with conventional silicon-based devices1. The ability to grow large, high-quality single crystals for 2D components-that is, conductors, semiconductors and insulators-is essential for the industrial application of 2D devices2-4. Atom-layered hexagonal boron nitride (hBN), with its excellent stability, flat surface and large bandgap, has been reported to be the best 2D insulator5-12. However, the size of 2D hBN single crystals is typically limited to less than one millimetre13-18, mainly because of difficulties in the growth of such crystals; these include excessive nucleation, which precludes growth from a single nucleus to large single crystals, and the threefold symmetry of the hBN lattice, which leads to antiparallel domains and twin boundaries on most substrates19. Here we report the epitaxial growth of a 100-square-centimetre single-crystal hBN monolayer on a low-symmetry Cu (110) vicinal surface, obtained by annealing an industrial copper foil. Structural characterizations and theoretical calculations indicate that epitaxial growth was achieved by the coupling of Cu <211> step edges with hBN zigzag edges, which breaks the equivalence of antiparallel hBN domains, enabling unidirectional domain alignment better than 99 per cent. The growth kinetics, unidirectional alignment and seamless stitching of the hBN domains are unambiguously demonstrated using centimetre- to atomic-scale characterization techniques. Our findings are expected to facilitate the wide application of 2D devices and lead to the epitaxial growth of broad non-centrosymmetric 2D materials, such as various transition-metal dichalcogenides20-23, to produce large single crystals.

Universal Imaging of Full Strain Tensor in 2D Crystals with Third-Harmonic Generation.

Quantitatively mapping and monitoring the strain distribution in 2D materials is essential for their physical understanding and function engineering. Optical characterization methods are always appealing due to unique noninvasion and high-throughput advantages. However, all currently available optical spectroscopic techniques have application limitation, e.g., photoluminescence spectroscopy is for direct-bandgap semiconducting materials, Raman spectroscopy is for ones with Raman-active and strain-sensitive phonon modes, and second-harmonic generation spectroscopy is only for noncentrosymmetric ones. Here, a universal methodology to measure the full strain tensor in any 2D crystalline material by polarization-dependent third-harmonic generation is reported. This technique utilizes the third-order nonlinear optical response being a universal property in 2D crystals and the nonlinear susceptibility has a one-to-one correspondence to strain tensor via a photoelastic tensor. The photoelastic tensor of both a noncentrosymmetric D3h WS2 monolayer and a centrosymmetric D3d WS2 bilayer is successfully determined, and the strain tensor distribution in homogenously strained and randomly strained monolayer WS2 is further mapped. In addition, an atlas of photoelastic tensors to monitor the strain distribution in 2D materials belonging to all 32 crystallographic point groups is provided. This universal characterization on strain tensor should facilitate new functionality designs and accelerate device applications in 2D-materials-based electronic, optoelectronic, and photovoltaic devices.

Sub-millimeter-Scale Growth of One-Unit-Cell-Thick Ferrimagnetic Cr2S3 Nanosheets.

Two-dimensional (2D) magnetic materials provide an ideal platform for the application in spintronic devices due to their unique spin states in nanometer scale. However, recent research on the exfoliated monolayer magnetic materials suffers from the instability in ambient atmosphere, which needs extraordinary protection. Hence the controllable synthesis of 2D magnetic materials with good quality and stability should be addressed. Here we report for the first time the van der Waals (vdW) epitaxial growth of one-unit-cell-thick air-stable ferrimagnet Cr2S3 semiconductor via a facile chemical vapor deposition method. Single crystal Cr2S3 with the domain size reaching to 200 µm is achieved. Most importantly, we observe the as grown Cr2S3 with a Néel temperature ( TN) of up to 120 K and a maximum saturation magnetic momentum of up to 65 µemu. As the temperature decreases, the samples show a transition from soft magnet to hard magnet with the highest coercivity of 1000 Oe. The one-unit-cell-thick Cr2S3 devices show a p-type transfer behavior with an on/off ratio over 103. Our work highlights Cr2S3 monolayer as an ideal magnetic semiconductor for 2D spintronic devices. The vdW epitaxy of nonlayered magnets introduces a new route for realizing magnetism in 2D limit and provides more application potential in the 2D spintronics.

Sub-10 nm stable graphene quantum dots embedded in hexagonal boron nitride.

Graphene quantum dots (GQDs), a zero-dimensional material system with distinct physical properties, have great potential in the applications of photonics, electronics, photovoltaics, and quantum information. In particular, GQDs are promising candidates for quantum computing. In principle, a sub-10 nm size is required for GQDs to present the intrinsic quantum properties. However, with such an extreme size, GQDs have predominant edges with lots of active dangling bonds and thus are not stable. Satisfying the demands of both quantum size and stability is therefore of great challenge in the design of GQDs. Herein we demonstrate the fabrication of sub-10 nm stable GQD arrays by embedding GQDs into large-bandgap hexagonal boron nitride (h-BN). With this method, the dangling bonds of GQDs were passivated by the surrounding h-BN lattice to ensure high stability, meanwhile maintaining their intrinsic quantum properties. The sub-10 nm nanopore array was first milled in h-BN using an advanced high-resolution helium ion microscope and then GQDs were directly grown in them through the chemical vapour deposition process. Stability analysis proved that the embedded GQDs show negligible property decay after baking at 100 °C in air for 100 days. The success in preparing sub-10 nm stable GQD arrays will promote the physical exploration and potential applications of this unique zero-dimensional in-plane quantum material.

Ultrafast Broadband Charge Collection from Clean Graphene/CH3NH3PbI3 Interface.

Photocarrier generation in a material, transportation to the material surface, and collection at the electrode interface are of paramount importance in any optoelectronic and photovoltaic device. In the last collection process, ideal performance comprises ultrafast charge collection to enhance current conversion efficiency and broadband collection to enhance energy conversion efficiency. Here, for the first time, we demonstrate ultrafast broadband charge collection achieved simultaneously at the clean graphene/organic-inorganic halide perovskite interface. The clean interface is realized by directly growing perovskite on graphene surface without polymer contamination. The tunable two-color pump-probe spectroscopy, time-resolved photoluminescence spectroscopy, and time-dependent density functional theory all reveal that the clean-interfacial graphene collects band-edge photocarriers of perovskite in an ultrashort time of ∼100 fs, with a current collection efficiency close to 99%. In addition, graphene can extract deep-band hot carriers of perovskite within only ∼50 fs, several orders faster than hot carrier relaxation and cooling in perovskite itself, due to the unique Dirac linear band structure of graphene, indicating a potential high energy conversion efficiency exceeding the Shockley-Queisser limit. Adding other graphene superiority of good transparency, high carrier mobility, and extreme flexibility, clean-interfacial graphene provides an ideal charge collection layer and electrode candidate for future optoelectronic and photovoltaic applications in two dimensions.