Intercalation in 2D materials and in situ studies.

Intercalation of atoms, ions and molecules is a powerful tool for altering or tuning the properties - interlayer interactions, in-plane bonding configurations, Fermi-level energies, electronic band structures and spin-orbit coupling - of 2D materials. Intercalation can induce property changes in materials related to photonics, electronics, optoelectronics, thermoelectricity, magnetism, catalysis and energy storage, unlocking or improving the potential of 2D materials in present and future applications. In situ imaging and spectroscopy technologies are used to visualize and trace intercalation processes. These techniques provide the opportunity for deciphering important and often elusive intercalation dynamics, chemomechanics and mechanisms, such as the intercalation pathways, reversibility, uniformity and speed. In this Review, we discuss intercalation in 2D materials, beginning with a brief introduction of the intercalation strategies, then we look into the atomic and intrinsic effects of intercalation, followed by an overview of their in situ studies, and finally provide our outlook.

Unusual Raman Enhancement Effect of Ultrathin Copper Sulfide.

In surface-enhanced Raman spectroscopy (SERS), 2D materials are explored as substrates owing to their chemical stability and reproducibility. However, they exhibit lower enhancement factors (EFs) compared to noble metal-based SERS substrates. This study demonstrates the application of ultrathin covellite copper sulfide (CuS) as a cost-effective SERS substrate with a high EF value of 7.2 × 104 . The CuS substrate is readily synthesized by sulfurizing a Cu thin film at room temperature, exhibiting a Raman signal enhancement comparable to that of an Au noble metal substrate of similar thickness. Furthermore, computational simulations using the density functional theory are employed and time-resolved photoluminescence measurements are performed to investigate the enhancement mechanisms. The results indicate that polar covalent bonds (Cu─S) and strong interlayer interactions in the ultrathin CuS substrate increase the probability of charge transfer between the analyte molecules and the CuS surface, thereby producing enhanced SERS signals. The CuS SERS substrate demonstrates the selective detection of various dye molecules, including rhodamine 6G, methylene blue, and safranine O. Furthermore, the simplicity of CuS synthesis facilitates large-scale production of SERS substrates with high spatial uniformity, exhibiting a signal variation of less than 5% on a 4-inch wafer.

Phase-Engineered WS2 Monolayer Quantum Dots by Rhenium Doping.

Transition metal dichalcogenides (TMDs) occur in the thermodynamically stable trigonal prismatic (2H) phase or the metastable octahedral (1T) phase. Phase engineering of TMDs has proven to be a powerful tool for applications in energy storage devices as well as in electrocatalysis. However, the mechanism of the phase transition in TMDs and the synthesis of phase-controlled TMDs remain challenging. Here we report the synthesis of Re-doped WS2 monolayer quantum dots (MQDs) using a simple colloidal chemical process. We find that the incorporation of a small amount of electron-rich Re atoms in WS2 changes the metal-metal distance in the 2H phase initially, which introduces strain in the structure (strained 2H (S2H) phase). Increasing the concentration of Re atoms sequentially transforms the S2H phase into the 1T and 1T' phases to release the strain. In addition, we performed controlled experiments by doping MoS2 with Re to distinguish between Re and Mo atoms in scanning transmission electron microscopy images and quantified the concentration range of Re atoms in each phase of MoS2, indicating that phase engineering of WS2 or MoS2 is possible by doping with different amounts of Re atoms. We demonstrate that the 1T' WS2 MQDs with 49 at. % Re show superior catalytic performance (a low Tafel slope of 44 mV/dec, a low overpotential of 158 mV at a current density of 10 mA/cm2, and long-term durability up to 5000 cycles) for the hydrogen evolution reaction. Our findings provide understanding and control of the phase transitions in TMDs, which will allow for the efficient manufacturing and translation of phase-engineered TMDs.

Comparative Studies of Atomically Thin Proton Conductive Films to Reduce Crossover in Hydrogen Fuel Cells.

Hydrogen fuel cells based on proton exchange membrane fuel cell (PEMFC) technology are promising as a source of clean energy to power a decarbonized future. However, PEMFCs are limited by a number of major inefficiencies; one of the most significant is hydrogen crossover. In this work, we comprehensively study the effects of two-dimensional (2D) materials applied to the anode side of the membrane as H2 barrier coatings on Nafion to reduce crossover effects on hydrogen fuel cells, while studying adverse effects on conductivity and catalyst performance in the beginning of life testing. The barrier layers studied include graphene, hexagonal boron nitride (hBN), amorphous boron nitride (aBN), and varying thicknesses of molybdenum disulfide (MoS2), all chosen due to their expected stability in a fuel cell environment. Crossover mitigation in the materials studied ranges from 4.4% (1 nm MoS2) to 46.1% (graphene) as compared to Nafion 211. Effects on proton conductivity are also studied, suggesting high areal proton transport in materials previously thought to be effectively nonconductive, such as 2 nm MoS2 and amorphous boron nitride under the conditions studied. The results indicate that a number of 2D materials are able to improve crossover effects, with those coated with 8 nm MoS2 and 1 L graphene able to achieve greater crossover reduction while minimizing conductivity penalty.

Langmuir-Blodgett Monolayer of Cobalt Phthalocyanine as Ultralow Loading Single-Atom Catalyst for Highly Efficient H2O2 Production.

The electrochemical production of H2O2 via the two-electron oxygen-reduction reaction (2e- ORR) has been actively studied using systems with atomically dispersed metal-nitrogen-carbon (M-N-C) structures. However, the development of well-defined M-N-C structures that restrict the migration and agglomeration of single-metal sites remains elusive. Herein, we demonstrate a Langmuir-Blodgett (LB) monolayer of cobalt phthalocyanine (CoPc) on monolayer graphene (LB CoPc/G) as a single-metal catalyst for the 2e- ORR. The as-prepared CoPc LB monolayer has a ß-form crystalline structure with a lattice space for the facile adsorption of oxygen molecules on the cobalt active sites. The CoPc LB monolayer system provides highly exposed Co atoms in a well-defined structure without agglomeration, resulting in significantly improved catalytic activity, which is manifested by a very high H2O2 production rate per catalyst (31.04 mol gcat-1 h-1) and TOF (36.5 s-1) with constant production stability for 24 hours. To the best of our knowledge, the CoPc LB monolayer system exhibits the highest H2O2 production rate per active site. This fundamental study suggests that an LB monolayer of molecules with single-metal atoms as a well-defined structure works for single-atom catalysts.

Photocatalysis with atomically thin sheets.

Atomically thin sheets (e.g., graphene and monolayer molybdenum disulfide) are ideal optical and reaction platforms. They provide opportunities for deciphering some important and often elusive photocatalytic phenomena related to electronic band structures and photo-charges. In parallel, in such thin sheets, fine tuning of photocatalytic properties can be achieved. These include atomic-level regulation of electronic band structures and atomic-level steering of charge separation and transfer. Herein, we review the physics and chemistry of electronic band structures and photo-charges, as well as their state-of-the-art characterization techniques, before delving into their atomic-level deciphering and mastery on the platform of atomically thin sheets.

2D Materials in the Display Industry: Status and Prospects.

With advances in flexible electronics, innovative foldable, rollable, and stretchable displays have been developed to maintain their performance under various deformations. These flexible devices can develop more innovative designs than conventional devices due to their light weight, high space efficiency, and practical convenience. However, developing flexible devices requires material innovation because the devices must be flexible and exhibit desirable electrical insulating/semiconducting/metallic properties. Recently, emerging 2D materials such as graphene, hexagonal boron nitride, and transition metal dichalcogenides have attracted considerable research attention because of their outstanding electrical, optical, and mechanical properties, which are ideal for flexible electronics. The recent progress and challenges of 2D material growth and display applications are reviewed and perspectives for exploring 2D materials for display applications are discussed.

P-type electrical contacts for 2D transition-metal dichalcogenides.

Digital logic circuits are based on complementary pairs of n- and p-type field effect transistors (FETs) via complementary metal oxide semiconductor technology. In three-dimensional (3D) or bulk semiconductors, substitutional doping of acceptor or donor impurities is used to achieve p- and n-type FETs. However, the controllable p-type doping of low-dimensional semiconductors such as two-dimensional (2D) transition-metal dichalcogenides (TMDs) has proved to be challenging. Although it is possible to achieve high-quality, low-resistance n-type van der Waals (vdW) contacts on 2D TMDs1-5, obtaining p-type devices by evaporating high-work-function metals onto 2D TMDs has not been realized so far. Here we report high-performance p-type devices on single- and few-layered molybdenum disulfide and tungsten diselenide based on industry-compatible electron beam evaporation of high-work-function metals such as palladium and platinum. Using atomic resolution imaging and spectroscopy, we demonstrate near-ideal vdW interfaces without chemical interactions between the 2D TMDs and 3D metals. Electronic transport measurements reveal that the Fermi level is unpinned and p-type FETs based on vdW contacts exhibit low contact resistance of 3.3 kΩ µm, high mobility values of approximately 190 cm2 V-1 s-1 at room temperature, saturation currents in excess of 10-5 A µm-1 and an on/off ratio of 107. We also demonstrate an ultra-thin photovoltaic cell based on n- and p-type vdW contacts with an open circuit voltage of 0.6 V and a power conversion efficiency of 0.82%.

Synthesis of 1T WSe2 on an Oxygen-Containing Substrate Using a Single Precursor.

The metallic property of metastable 1T' WSe2 and its promising catalytic performance have attracted considerable interest. A hot injection method has been used to synthesize 1T' WSe2 with a three-dimensional morphology; however, this method requires two or more precursors and long-chain ligands, which inhibit the catalytic performance. Here, we demonstrate the synthesis of 1T' WSe2 on a substrate by a simple heating-up method using a single precursor, tetraethylammonium tetraselenotungstate [(Et4N)2WSe4]. The triethylamine produced after the reaction is an electron donor that yields negatively charged WSe2, which is stabilized by triethylammonium cations as intercalants between layers and induces 1T' WSe2. The purity of 1T' WSe2 is higher on oxygen-containing crystalline substrates than amorphous substrates because the strong adhesion between WSe2 and the substrate can produce sufficient triethylammonium (TEA) intercalation. Among the oxygen-containing crystal substrates, the substrate with a lower lattice mismatch with 1T' WSe2 showed higher 1T' purity due to the uniform TEA intercalation. Furthermore, 1T' WSe2 on carbon cloth exhibited a more enhanced catalytic performance in the hydrogen evolution reaction (197 mV at 10 mA/cm2) than has been reported previously.

Epitaxial single-crystal hexagonal boron nitride multilayers on Ni (111).

Large-area single-crystal monolayers of two-dimensional (2D) materials such as graphene1-3, hexagonal boron nitride (hBN)4-6 and transition metal dichalcogenides7,8 have been grown. hBN is considered to be the 'ideal' dielectric for 2D-materials-based field-effect transistors (FETs), offering the potential for extending Moore's law9,10. Although hBN thicker than a monolayer is more desirable as substrate for 2D semiconductors11,12, highly uniform and single-crystal multilayer hBN growth has yet to be demonstrated. Here we report the epitaxial growth of wafer-scale single-crystal trilayer hBN by a chemical vapour deposition (CVD) method. Uniformly aligned hBN islands are found to grow on single-crystal Ni (111) at early stage and finally to coalesce into a single-crystal film. Cross-sectional transmission electron microscopy (TEM) results show that a Ni23B6 interlayer is formed (during cooling) between the single-crystal hBN film and Ni substrate by boron dissolution in Ni. There are epitaxial relationships between hBN and Ni23B6 and between Ni23B6 and Ni. We also find that the hBN film acts as a protective layer that remains intact during catalytic evolution of hydrogen, suggesting continuous single-crystal hBN. This hBN transferred onto the SiO2 (300 nm)/Si wafer acts as a dielectric layer to reduce electron doping from the SiO2 substrate in MoS2 FETs. Our results demonstrate high-quality single-crystal  multilayered hBN over large areas, which should open up new pathways for making it a ubiquitous substrate for 2D semiconductors.

Facile preparation of aqueous-soluble fluorescent polyethylene glycol functionalized carbon dots from palm waste by one-pot hydrothermal carbonization for colon cancer nanotheranostics.

Carbon dots (CDs) are categorized as an emerging class of zero-dimension nanomaterials having high biocompatibility, photoluminescence, tunable surface, and hydrophilic property. CDs, therefore, are currently of interest for bio-imaging and nano-medicine applications. In this work, polyethylene glycol functionalized CDs (CD-PEG) were prepared from oil palm empty fruit bunch by a one-pot hydrothermal technique. PEG was chosen as a passivating agent for the enhancement of functionality and photoluminescence properties of CDs. To prepare the CDs-PEG, the effects of temperature, time, and concentration of PEG were investigated on the properties of CDs. The as-prepared CDs-PEG were characterized by several techniques including dynamic light scattering, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, fluorescence spectroscopy, Raman spectroscopy, Fourier-transform infrared spectroscopy and Thermogravimetric analysis. The as-prepared CDs under hydrothermal condition at 220 °C for 6 h had spherical morphology with an average diameter of 4.47 nm. Upon modification, CDs-PEG were photo-responsive with excellent photoluminescence property. The CDs-PEG was subsequently used as a drug carrier for doxorubicin [DOX] delivery to CaCo-2, colon cancer cells in vitro. DOX was successfully loaded onto CDs-PEG surface confirmed by FT-IR and Matrix-Assisted Laser Desorption/Ionization Time-of-Flight Mass Spectrometer (MALDI-TOF/MS) patterns. The selective treatment of CDs-PEG-DOX against the colorectal cancer cells, , relative to normal human fibroblast cells was succesfully demonstrated.

High-yield production of mono- or few-layer transition metal dichalcogenide nanosheets by an electrochemical lithium ion intercalation-based exfoliation method.

Transition metal dichalcogenide (TMD) nanomaterials, especially the mono- or few-layer ones, have received extensive research interest owing to their versatile properties, ranging from true metals (e.g., NbS2 and VSe2) and semimetals (e.g., WTe2 and TiSe2) to semiconductors (e.g., MoS2 and We2) and insulators (e.g., HfS2). Therefore, the reliable production of these nanomaterials with atomically thin thickness and laterally uniform dimension is essential for their promising applications in transistors, photodetectors, electroluminescent devices, catalysis, energy conversion, environment remediation, biosensing, bioimaging, and so on. Recently, the electrochemical lithium ion intercalation-based exfoliation method has emerged as a mature, efficient and promising strategy for the high-yield production of mono- or few-layer TMD nanosheets; monolayer MoS2 (yield of 92%), monolayer TaS2 (yield of 93%) and bilayer TiS2 (yield of 93%) with lateral dimensions of ~1 µm (refs. 1-3). This Protocol describes the details of experimental procedures for the high-yield synthesis of mono- or few-layer TMDs and other inorganic nanosheets such as MoS2, WS2, TiS2, TaS2, ZrS2, graphene, h-BN, NbSe2, WSe2, Sb2Se3 and Bi2Te3 by using the electrochemical lithium ion intercalation-based exfoliation method, which involves the electrochemical intercalation of lithium ions into layered inorganic crystals and a mild sonication process. The whole protocol takes 26-38 h for the successful production of ultrathin inorganic nanosheets.

Synthesis of metallic mixed 3R and 2H Nb1+xS2 nanoflakes by chemical vapor deposition.

In this work, we report the synthesis and characterization of mixed phase Nb1+xS2 nanoflakes prepared by chemical vapor deposition. The as-grown samples show a high density of flakes (thickness ∼50 nm) that form a continuous film. Raman and X-ray diffraction data show that the samples consist of both 2H and 3R phases, with the 2H phase containing a high concentration of Nb interstitials. These Nb interstitials sit in between the NbS2 layers to form Nb1+xS2. Cross-sectional Energy Dispersive Spectroscopy analysis with transmission electron microscopy suggests that the 2H Nb1+xS2 region is found in thinner flakes, while 3R NbS2 is observed in thicker regions of the films. The evolution of the phase from 2H Nb1+xS2 to 3R NbS2 may be attributed to the change of the growth environment from Nb-rich at the start of the growth to sulfur-rich at the latter stage. It was also found that the incorporation of Nb interstitials is highly dependent on the temperature of the NbCl5 precursor and the position of the substrate in the furnace. Samples grown at high NbCl5 temperature and with substrate located closer to the NbCl5 source show higher incorporation of Nb interstitials. Electrical measurements show linear I-V characteristics, indicating the metallic nature of the Nb1+xS2 film with relatively low resistivity of 4.1 × 10-3Ω cm.

Radio-frequency-transmitting hexagonal boron nitride-based anti- and de-icing heating system.

Anti- and de-icing heating systems are used to both prevent the accumulation of ice and to remove it and thus avoid damage. Typically, anti- and de-icing heating systems employ carbon-based materials, metal frames, and bulky ceramic structures. These structures generally lead to the loss of radio-frequency (RF) signals and are also relatively heavy. Therefore, RF equipment such as radar domes (radomes) and antennas require anti- and de-icing systems with high RF transmittance for normal operation. In this work, we fabricated a fluorine-doped tin oxide (FTO) wave pattern covered with hexagonal boron nitride (h-BN) layers (i.e., an h-BN/FTO wave pattern) on a glass substrate for use as an RF-transmitting heating system for anti- and de-icing. The FTO wave pattern and h-BN layer act as the heating element and heat spreader, respectively. The h-BN layer showed a transmittance of approximately 90% for RF waves on glass (X band: 8.2-12.4 GHz) (the 10% loss was attributable to the glass substrate). The differences in the temperatures of the FTO-patterned and non-patterned areas for the h-BN(3.6 nm)/FTO and FTO wave pattern were 19.3 and 25.5 °C, respectively. This means that the h-BN layer improved the heat-spreading performance by 6.2 °C. Furthermore, a de-icing test was performed using the h-BN(3.6 nm)/FTO wave pattern by applying a voltage of 40 V at -20 °C. The ice on the non-patterned area melted within 1 min while that on the FTO-patterned area melted within 30 s. These results suggest that the fabricated h-BN(3.6 nm)/FTO wave pattern for RF-transmitting heating systems is suitable for use with the radomes of drones, unmanned aerial vehicles, aircraft, and spaceships in extremely cold environments.

Blue emission at atomically sharp 1D heterojunctions between graphene and h-BN.

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.

Ultralow-dielectric-constant amorphous boron nitride.

Decrease in processing speed due to increased resistance and capacitance delay is a major obstacle for the down-scaling of electronics1-3. Minimizing the dimensions of interconnects (metal wires that connect different electronic components on a chip) is crucial for the miniaturization of devices. Interconnects are isolated from each other by non-conducting (dielectric) layers. So far, research has mostly focused on decreasing the resistance of scaled interconnects because integration of dielectrics using low-temperature deposition processes compatible with complementary metal-oxide-semiconductors is technically challenging. Interconnect isolation materials must have low relative dielectric constants (κ values), serve as diffusion barriers against the migration of metal into semiconductors, and be thermally, chemically and mechanically stable. Specifically, the International Roadmap for Devices and Systems recommends4 the development of dielectrics with κ values of less than 2 by 2028. Existing low-κ materials (such as silicon oxide derivatives, organic compounds and aerogels) have κ values greater than 2 and poor thermo-mechanical properties5. Here we report three-nanometre-thick amorphous boron nitride films with ultralow κ values of 1.78 and 1.16 (close to that of air, κ = 1) at operation frequencies of 100 kilohertz and 1 megahertz, respectively. The films are mechanically and electrically robust, with a breakdown strength of 7.3 megavolts per centimetre, which exceeds requirements. Cross-sectional imaging reveals that amorphous boron nitride prevents the diffusion of cobalt atoms into silicon under very harsh conditions, in contrast to reference barriers. Our results demonstrate that amorphous boron nitride has excellent low-κ dielectric characteristics for high-performance electronics.

Spatially controlled lateral heterostructures of graphene and transition metal dichalcogenides toward atomically thin and multi-functional electronics.

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.

General Colloidal Synthesis of Transition-Metal Disulfide Nanomaterials as Electrocatalysts for Hydrogen Evolution Reaction.

The material-efficient monolayers of transition-metal dichalcogenides (TMDs) are a promising class of ultrathin nanomaterials with properties ranging from insulating through semiconducting to metallic, opening a wide variety of their potential applications from catalysis and energy storage to optoelectronics, spintronics, and valleytronics. In particular, TMDs have a great potential as emerging inexpensive alternatives to noble metal-based catalysts in electrochemical hydrogen evolution. Herein, we report a straightforward, low-cost, and general colloidal synthesis of various 2D transition-metal disulfide nanomaterials, such as MoS2, WS2, NiSx, FeSx, and VS2, in the absence of organic ligands. This new preparation route provides many benefits including relatively mild reaction conditions, high reproducibility, high yields, easy upscaling, no post-thermal annealing/treatment steps to enhance the catalytic activity, and, finally, especially for molybdenum disulfide nanosheets, high activity in the hydrogen evolution reaction. To underline the universal application of the synthesis, we prepared mixed CoxMo1-xS2 nanosheets in one step to optimize the catalytic activity of pure undoped MoS2, which resulted in an enhanced hydrogen evolution reaction performance characterized by onset potentials as low as 134 mV and small Tafel slopes of 55 mV/dec.