Alkali metal bilayer intercalation in graphene.

Alkali metal (AM) intercalation between graphene layers holds promise for electronic manipulation and energy storage, yet the underlying mechanism remains challenging to fully comprehend despite extensive research. In this study, we employ low-voltage scanning transmission electron microscopy (LV-STEM) to visualize the atomic structure of intercalated AMs (potassium, rubidium, and cesium) in bilayer graphene (BLG). Our findings reveal that the intercalated AMs adopt bilayer structures with hcp stacking, and specifically a C6M2C6 composition. These structures closely resemble the bilayer form of fcc (111) structure observed in AMs under high-pressure conditions. A negative charge transferred from bilayer AMs to graphene layers of approximately 1~1.5×1014 e-/cm-2 was determined by electron energy loss spectroscopy (EELS), Raman, and electrical transport. The bilayer AM is stable in BLG and graphite superficial layers but absent in the graphite interior, primarily dominated by single-layer AM intercalation. This hints at enhancing AM intercalation capacity by thinning the graphite material.

Molybdenum Chloride Nanostructures with Giant Lattice Distortions Intercalated into Bilayer Graphene.

The nanospace of the van der Waals (vdW) gap between structural units of two-dimensional (2D) materials serves as a platform for growing unusual 2D systems through intercalation and studying their properties. Various kinds of metal chlorides have previously been intercalated for tuning the properties of host layered materials, but the atomic structure of the intercalants remains still unidentified. In this study, we investigate the atomic structural transformation of molybdenum(V) chloride (MoCl5) after intercalation into bilayer graphene (BLG). Using scanning transmission electron microscopy, we found that the intercalated material represents MoCl3 networks, MoCl2 chains, and Mo5Cl10 rings. Giant lattice distortions and frequent structural transitions occur in the 2D MoClx that have never been observed in metal chloride systems. The trend of symmetric to nonsymmetric structural transformations can cause additional charge transfer from BLG to the intercalated MoClx, as suggested by our density functional theory calculations. Our study deepens the understanding of the behavior of matter in the confined space of the vdW gap in BLG and provides hints at a more efficient tuning of material properties by intercalation for potential applications, including transparent conductive films, optoelectronics, and energy storage.

Random but limited pressure of graphene liquid cells.

Even though many researchers have used graphene liquid cells for atomic-resolution observation of liquid samples in the last decade, no one has yet simultaneously measured their three-dimensional shape and pressure. In this study, we have done so with an atomic force microscope, for cells with base radii of 20-134 nm and height of 3.9-21.2 nm. Their inner pressure ranged from 1.0 to 63 MPa but the maximum value decreased as the base radius increased. We discuss the mechanism that results in this inverse relationship by introducing an adhesive force between the graphene membranes. Also, the sample preparation procedure used in this experiment is highly reproducible and transferable to a wide variety of substrates.

Surface etching and edge control of hexagonal boron nitride assisted by triangular Sn nanoplates.

Hexagonal boron nitride (hBN) is an ideal insulating substrate and template for other two-dimensional (2D) materials. The combination of hBN and 2D materials of group IV atoms, such as graphene, is interesting, because it can offer attractive physical properties and promising applications. Here, we demonstrate the unique behavior of tin (Sn), one of the group IV elements, on multilayer hBN which was grown by chemical vapor deposition (CVD). At high temperatures, triangular nanoplates formed after thermal deposition of Sn on the hBN surface, with their orientations determined by the hBN lattice. The triangular Sn nanoplates moved on the hBN surface, leaving monolayer-deep nanotrenches. Low-energy electron microscopy (LEEM) revealed that the nanotrenches are aligned in the armchair directions of the hBN. Furthermore, an additional Ar annealing without supplying Sn vapor induced the structural change of the linear trenches to triangular pits, indicating the preferential formation of zigzag edges in the absence of Sn. Our work highlights the unique behavior of Sn on hBN and offers a novel route to engineer the hBN surface.

Twist Angle-Dependent Molecular Intercalation and Sheet Resistance in Bilayer Graphene.

Bilayer graphene (BLG) has a two-dimensional (2D) interlayer nanospace that can be used to intercalate molecules and ions, resulting in a significant change of its electronic and magnetic properties. Intercalation of BLG with different materials, such as FeCl3, MoCl5, Li ions, and Ca ions, has been demonstrated. However, little is known about how the twist angle of the BLG host affects intercalation. Here, by using artificially stacked BLG with controlled twist angles, we systematically investigated the twist angle dependence of intercalation of metal chlorides. We discovered that BLG with high twist angles of >15° is more favorable for intercalation than BLG with low twist angles. Density functional theory calculations suggested that the weaker interlayer coupling in high twist angle BLG is the key for effective intercalation. Scanning transmission electron microscope observations revealed that co-intercalation of AlCl3 and CuCl2 molecules into BLG gives various 2D structures in the confined interlayer nanospace. Moreover, before intercalation we observed a significantly lower sheet resistance in BLG with high twist angles (281 ± 98 Ω/□) than that in AB stacked BLG (580 ± 124 Ω/□). Intercalation further decreased the sheet resistance, reaching values as low as 48 Ω/□, which is the lowest value reported so far for BLG. This work provides a twist angle-dependent phenomenon, in which enhanced intercalation and drastic changes of the electrical properties can be realized by controlling the stacking angle of adjacent graphene layers.

Science of 2.5 dimensional materials: paradigm shift of materials science toward future social innovation.

The past decades of materials science discoveries are the basis of our present society - from the foundation of semiconductor devices to the recent development of internet of things (IoT) technologies. These materials science developments have depended mainly on control of rigid chemical bonds, such as covalent and ionic bonds, in organic molecules and polymers, inorganic crystals and thin films. The recent discovery of graphene and other two-dimensional (2D) materials offers a novel approach to synthesizing materials by controlling their weak out-of-plane van der Waals (vdW) interactions. Artificial stacks of different types of 2D materials are a novel concept in materials synthesis, with the stacks not limited by rigid chemical bonds nor by lattice constants. This offers plenty of opportunities to explore new physics, chemistry, and engineering. An often-overlooked characteristic of vdW stacks is the well-defined 2D nanospace between the layers, which provides unique physical phenomena and a rich field for synthesis of novel materials. Applying the science of intercalation compounds to 2D materials provides new insights and expectations about the use of the vdW nanospace. We call this nascent field of science '2.5 dimensional (2.5D) materials,' to acknowledge the important extra degree of freedom beyond 2D materials. 2.5D materials not only offer a new field of scientific research, but also contribute to the development of practical applications, and will lead to future social innovation. In this paper, we introduce the new scientific concept of this science of '2.5D materials' and review recent research developments based on this new scientific concept.

Coupling and Decoupling of Bilayer Graphene Monitored by Electron Energy Loss Spectroscopy.

We studied the interlayer coupling and decoupling of bilayer graphene (BLG) using spatially resolved electron energy loss spectroscopy with a monochromated electron source. We correlated the twist-angle-dependent energy band hybridization with Moiré superlattices and the corresponding optical absorption peaks. The optical absorption peak originates from the excitonic transition between the hybridized van Hove singularities (vHSs), which shifts systematically with the twist angle. We then proved that the BLG decouples when a monolayer of metal chloride is intercalated in its van der Waals gap and results in the elimination of the vHS peak.

Polymorphic Phases of Metal Chlorides in the Confined 2D Space of Bilayer Graphene.

Unprecedented 2D metal chloride structures are grown between sheets of bilayer graphene through intercalation of metal and chlorine atoms. Numerous spatially confined 2D phases of AlCl3 and CuCl2 distinct from their typical bulk forms are found, and the transformations between these new phases under the electron beam are directly observed by in situ scanning transmission electron microscopy (STEM). The density functional theory calculations confirm the metastability of the atomic structures derived from the STEM experiments and provide insights into the electronic properties of the phases, which range from insulators to semimetals. Additionally, the co-intercalation of different metal chlorides is found to create completely new hybrid systems; in-plane quasi-1D AlCl3 /CuCl2 heterostructures are obtained. The existence of polymorphic phases hints at the unique possibilities for fabricating new types of 2D materials with diverse electronic properties confined between graphene sheets.

Pinning in a Contact and Noncontact Manner: Direct Observation of a Three-Phase Contact Line Using Graphene Liquid Cells.

Pinning of a three-phase contact line at the nanoscale cannot be explained by conventional macroscale theories and thus requires an experimental insight to understand this phenomenon. We performed in-situ transmission electron microscopy observation of the three-phase contact lines of bubbles inside graphene liquid cells to experimentally investigate the causes of nanoscale pinning. In our observations, the three-phase contact line was not affected by the 0.6 nm-thick inhomogeneity of the graphene surface, but thicker metal nanoparticles with diameters of 2-10 nm and nanoflakes caused pinning of the gas-liquid interface. Notably, we found that flake-like objects can cause pinning that prevents the bubble overcome the flake object in a noncontact state, with a 2 nm-thick liquid film between them and the bubble. This phenomenon can be explained by the repulsive force obtained using the Derjaguin, Landau, Verwey, and Overbeek theory. We also observed that the flake temporally prevented the gas-liquid interface moving away from the flake. We discussed the physical mechanism of the attractive force-like phenomenon by considering the nanoconfinement effect of the liquid sandwiched by two graphene sheets and the hydration layer formed near the solid surface.

One-step vapour phase growth of two-dimensional formamidinium-based perovskite and its hot carrier dynamics.

Formamidinum lead iodide perovskite is one of the most promising materials for application in solar cells due to its narrow band gap and higher thermal stability. In this work, we demonstrate the facile synthesis of square-shaped formamidinium lead iodide single crystals on indium tin oxide (ITO) substrates using a one-step vapour phase deposition method. Formamidinium lead iodide-based two-dimensional layered perovskite crystals were successfully synthesized by controlling the deposition conditions. These crystals exhibited a blue-shifted photoluminescence (PL) compared to the conventional formaminium lead iodide perovskite crystals. Power law fittings of the excitation power dependent PL spectra revealed that Auger heating becomes dominant at high excitation densities. In addition, we observed an asymmetric broadening of the PL peak tail at the high energy side, indicating light emission from hot carriers even under steady-state illumination conditions. Phonon-bottleneck effect and Auger heating were considered as the main mechanisms for retardation of hot carrier cooling. Further analysis of the high energy tails using Maxwell-Boltzmann fitting revealed hot-carrier temperatures as high as 690 K. Our findings provide an important aspect of the synthetic approach of perovskites for their potential application in hot carrier solar cells.

Isothermal Growth and Stacking Evolution in Highly Uniform Bernal-Stacked Bilayer Graphene.

Controlling the stacking order in bilayer graphene (BLG) allows realizing interesting physical properties. In particular, the possibility of tuning the band gap in Bernal-stacked (AB) BLG (AB-BLG) has a great technological importance for electronic and optoelectronic applications. Most of the current methods to produce AB-BLG suffer from inhomogeneous layer thickness and/or coexistence with twisted BLG. Here, we demonstrate a method to synthesize highly pure large-area AB-BLG by chemical vapor deposition using Cu-Ni films. Increasing the reaction time resulted in a gradual increase of the AB stacking, with the BLG eventually free from twist regions for the longer growth times (99.4% of BLG has AB stacking), due to catalyst-assisted continuous BLG reconstruction driven by carbon dissolution-segregation processes. The band gap opening was confirmed by the electrical measurements on field-effect transistors using two different device configurations. The concept of the continuous reconstruction to achieve highly pure AB-BLG offers a way to control the stacking order of catalytically grown two-dimensional materials.

Nanoscale Bubble Dynamics Induced by Damage of Graphene Liquid Cells.

Graphene liquid cells provide the highest possible spatial resolution for liquid-phase transmission electron microscopy. Here, in graphene liquid cells (GLCs), we studied the nanoscale dynamics of bubbles induced by controllable damage in graphene. The extent of damage depended on the electron dose rate and the presence of bubbles in the cell. After graphene was damaged, air leaked from the bubbles into the water. We also observed the unexpected directional nucleation of new bubbles, which is beyond the explanation of conventional diffusion theory. We attributed this to the effect of nanoscale confinement. These findings provide new insights into complex fluid phenomena under nanoscale confinement.

Scanning Moiré Fringe Method: A Superior Approach to Perceive Defects, Interfaces, and Distortion in 2D Materials.

Scanning moiré fringe (SMF) is a widely utilized technique for the precise measurement of the strain field in semiconductor transistors and heterointerfaces. With the growing challenges of traditional chip scaling, two-dimensional (2D) materials turn out to be ideal candidates for incorporation into semiconductor devices. Therefore, a method to efficiently locate defects and grain boundaries in 2D materials is highly essential. Here, we present a demonstration of using the SMF method to locate the domain boundaries at the nearly coherent interfaces with sub-angstrom spatial resolution under submicron fields of views. The strain field of small angle grain boundary and lateral heterojunction are instantaneously found and precisely determined by a quick SMF method without any atomic resolution images.

Vapor Phase Selective Growth of Two-Dimensional Perovskite/WS2 Heterostructures for Optoelectronic Applications.

Organic-inorganic hybrid perovskites have attracted increased interest owing to their exceptional optoelectronic properties and promising applications. Monolayers of transition metal dichalcogenides (TMDCs), such as tungsten disulfide (WS2), are also intriguing because of their unique optoelectronic properties and their atomically thin and flexible structures. Therefore, the combination of these different types of materials is very attractive in terms of fundamental science of interface interaction, as well as for the realization of ultrathin optoelectronic devices with high performance. Here, we demonstrate the controlled synthesis of two-dimensional (2D) perovskite/WS2 heterostructures by an all vapor-phase growth approach. This involves the chemical vapor deposition (CVD) growth of monolayer WS2, followed by the vapor-phase selective deposition of 2D PbI2 onto the WS2 with the successive conversion of PbI2 to organic-inorganic perovskite (CH3NH3PbI3). Moreover, the selective growth of the perovskite on prepatterned WS2 enables the direct synthesis of patterned heterostructures, avoiding any damage to the perovskite. The photodetectors utilizing the perovskite/WS2 heterostructure show increased responsivities compared with isolated thin perovskite obtained by conventional solution methods. The integration of 2D perovskite with TMDCs opens a new avenue to fabricate advanced devices by combining their unique properties and overcoming current processing difficulties of perovskites.

Chemically Tuned p- and n-Type WSe2 Monolayers with High Carrier Mobility for Advanced Electronics.

Monolayers of transition metal dichalcogenides (TMDCs) have attracted a great interest for post-silicon electronics and photonics due to their high carrier mobility, tunable bandgap, and atom-thick 2D structure. With the analogy to conventional silicon electronics, establishing a method to convert TMDC to p- and n-type semiconductors is essential for various device applications, such as complementary metal-oxide-semiconductor (CMOS) circuits and photovoltaics. Here, a successful control of the electrical polarity of monolayer WSe2 is demonstrated by chemical doping. Two different molecules, 4-nitrobenzenediazonium tetrafluoroborate and diethylenetriamine, are utilized to convert ambipolar WSe2 field-effect transistors (FETs) to p- and n-type, respectively. Moreover, the chemically doped WSe2 show increased effective carrier mobilities of 82 and 25 cm2 V-1 s-1 for holes and electrons, respectively, which are much higher than those of the pristine WSe2 . The doping effects are studied by photoluminescence, Raman, X-ray photoelectron spectroscopy, and density functional theory. Chemically tuned WSe2 FETs are integrated into CMOS inverters, exhibiting extremely low power consumption (≈0.17 nW). Furthermore, a p-n junction within single WSe2 grain is realized via spatially controlled chemical doping. The chemical doping method for controlling the transport properties of WSe2 will contribute to the development of TMDC-based advanced electronics.

Synthesis of sub-millimeter single-crystal grains of aligned hexagonal boron nitride on an epitaxial Ni film.

Hexagonal boron nitride (h-BN), an insulating two-dimensional (2D) layered material, has attracted increasing interest due to its electrical screening effect, high-temperature-resistant gas barrier properties, and other unique applications. However, the presence of grain boundaries (GBs) in h-BN is a hindrance to obtain these properties. Here, we demonstrate the epitaxial growth of monolayer h-BN by chemical vapor deposition (CVD) on Ni(111) thin films deposited on c-plane sapphire. The Ni(111) films showed higher thermal stability than Cu(111) and Cu-Ni(111) alloy films, allowing us to perform CVD growth at a high temperature of 1100 °C. This resulted in an increase of the h-BN grain sizes to up to 0.5 millimeter, among the highest reported so far, and in a well-defined triangular grain shape. Low-energy electron microscopy (LEEM) revealed the epitaxial relationship between h-BN and the underlying Ni(111) lattice, leading to a preferential alignment of the h-BN grains. Both the large grain size and the alignment are expected to facilitate the synthesis of h-BN with a low density of GBs. We also found that the addition of N2 gas during the CVD improves the crystalline shape of the h-BN grains, changing from an irregular, truncated to a sharp triangle. The growth behavior of monolayer h-BN is further discussed in terms of the dependences on growth temperature and pressure, as well as on the structural evolution of the Ni metal catalyst. Our findings not only help understand the h-BN growth mechanism but also offer a new route to grow high-quality, monolayer h-BN films.

A novel graphene barrier against moisture by multiple stacking large-grain graphene.

The moisture barrier properties of stacked graphene layers on Cu surfaces were investigated with the goal of improving the moisture barrier efficiency of single-layer graphene (SLG) for Cu metallization. SLG with large grain size were stacked on Cu surfaces coated with CVD-SLG to cover the grain-boundaries and defective areas of the underneath SLG film, which was confirmed to be oxidized by Raman spectroscopy measurements. To evaluate the humidity resistance of the graphene-coated Cu surfaces, temperature humidity storage (THS) testing was conducted under accelerated oxidation conditions (85 °C and 85% relative humidity) for 100 h. The color changes of the Cu surfaces during THS testing were observed by optical microscopy, while the oxidized Cu into Cu2O and CuO was detected by X-ray photoelectron spectroscopy (XPS). The experimental results were accord with the results of first-principle simulation for the energetic barrier against water diffusion through the stacked graphene layers with different overlap. The results demonstrate the efficiency of SLG stacking approach against moisture for Cu metallization.

van der Waals interaction-induced photoluminescence weakening and multilayer growth in epitaxially aligned WS2.

Recently, transition metal dichalcogenides (TMDCs) have attracted great interest due to their unique electronic and optical properties. Chemical vapor deposition (CVD) has been regarded as the most promising method for the synthesis of large-area TMDCs with high reproducibility. Having similar hexagonal crystal structures with many TMDCs, c-plane sapphire is commonly used as a growth substrate in CVD. However, few studies have been reported on the influence of the sapphire substrate on the growth behavior and physical properties of TMDCs. In this work, we demonstrate that higher strain is induced in epitaxially grown WS2 grains via van der Waals interactions with sapphire as compared with misaligned WS2 grains. In addition, this strain was found to enhance overlayer deposition on monolayer WS2, while multilayer growth was not observed in non-epitaxial WS2. Photoluminescence (PL) of the epitaxially grown WS2 grains was reduced, reflecting the effective van der Waals interaction with sapphire. Moreover, low-temperature PL measurements revealed strong influence of the c-plane sapphire surface on the optical properties of WS2. Density functional theory (DFT) calculation supports that the aligned WS2 grains are more strongly bound to the sapphire surface, as compared with misaligned WS2. Our work offers a new insight into the understanding of the influence of the substrate on the CVD-grown TMDC materials.

Surface-Mediated Aligned Growth of Monolayer MoS2 and In-Plane Heterostructures with Graphene on Sapphire.

Aligned growth of transition metal dichalcogenides and related two-dimensional (2D) materials is essential for the synthesis of high-quality 2D films due to effective stitching of merging grains. Here, we demonstrate the controlled growth of highly aligned molybdenum disulfide (MoS2) on c-plane sapphire with two distinct orientations, which are highly controlled by tuning sulfur concentration. We found that the size of the aligned MoS2 grains is smaller and their photoluminescence is weaker as compared with those of the randomly oriented grains, signifying enhanced MoS2-substrate interaction in the aligned grains. This interaction induces strain in the aligned MoS2, which can be recognized from their high susceptibility to air oxidation. The surface-mediated MoS2 growth on sapphire was further developed to the rational synthesis of an in-plane MoS2-graphene heterostructure connected with the predefined orientation. The in-plane epitaxy was observed by low-energy electron microscopy. Transmission electron microscopy and scanning transmission electron microscopy suggest the alignment of a zigzag edge of MoS2 parallel to a zigzag edge of the neighboring graphene. Moreover, better electrical contact to MoS2 was obtained by the monolayer graphene compared with a conventional metal electrode. Our findings deepen the understanding of the chemical vapor deposition growth of 2D materials and also contribute to the tailored synthesis as well as applications of advanced 2D heterostructures.

Controlled Growth of Large-Area Uniform Multilayer Hexagonal Boron Nitride as an Effective 2D Substrate.

Multilayer hexagonal boron nitride (h-BN) is an ideal insulator for two-dimensional (2D) materials, such as graphene and transition metal dichalcogenides, because h-BN screens out influences from surroundings, allowing one to observe intrinsic physical properties of the 2D materials. However, the synthesis of large and uniform multilayer h-BN is still very challenging because it is difficult to control the segregation process of B and N atoms from metal catalysts during chemical vapor deposition (CVD) growth. Here, we demonstrate CVD growth of multilayer h-BN with high uniformity by using the Ni-Fe alloy film and borazine (B3H6N3) as catalyst and precursor, respectively. Combining Ni and Fe metals tunes the solubilities of B and N atoms and, at the same time, allows one to engineer the metal crystallinity, which stimulates the uniform segregation of multilayer h-BN. Furthermore, we demonstrate that triangular WS2 grains grown on the h-BN show photoluminescence stronger than that grown on a bare SiO2 substrate. The PL line width of WS2/h-BN (the minimum and mean widths are 24 and 43 meV, respectively) is much narrower than those of WS2/SiO2 (44 and 67 meV), indicating the effectiveness of our CVD-grown multilayer h-BN as an insulating layer. Large-area, multilayer h-BN realized in this work will provide an excellent platform for developing practical applications of 2D materials.