Band Gap Engineering of MoxW1-xS2 Alloy Monolayers with Wafer-Scale Uniformity.

Modulating the band gap of two-dimensional (2D) transition metal dichalcogenide (TMDC) semiconductors is critical for their application in a wider spectral range. Alloying has been demonstrated as an effective method for regulating the band gap of 2D TMDC semiconductors. The fabrication of large-area 2D TMDC alloy films with centimeter-scale uniformity is fundamental to the application of integrated devices. Herein, we report a liquid-phase precursor one-step chemical vapor deposition (CVD) method for fabricating a MoxW1-xS2 alloy monolayer with a large size and an adjustable band gap. Good crystalline quality and high uniformity on a wafer scale enable the continuous adjustment of its band gap in the range of 1.8-2.0 eV. Density functional theory calculations provided a deep understanding of the Raman-active vibration modes of the MoxW1-xS2 alloy monolayer and the change in the conductivity of the alloy with photon energy. The synthesis of large-area MoxW1-xS2 alloy monolayers is a critical step toward the application of 2D layered semiconductors in practical optoelectronic devices.

Angle-Resolved Optical Imaging of Interlayer Rotations in Twisted Bilayer Graphene.

Twisted bilayer graphene (TBG) is a prototypical layered material whose properties are strongly correlated to interlayer coupling. The two stacked graphene layers with distinct orientations are investigated to generate peculiar optical and electronic phenomena. Thus, the rapid, reliable, and nondestructive twist angle identification technique is of essential importance. Here, we integrated the white light reflection spectra (WLRS), the Raman spectroscopy, and the transmission electron microscope (TEM) to propose a facile RGB optical imaging technique that identified the twist angle of the TBG in a large area intuitively with high efficiency. The RGB technique established a robust correlation between the interlayer rotation angle and the contrast difference in the RGB color channels of a standard optical image. The angle-resolved optical behavior is attributed to the absorption resonance matching with the separation of van Hove singularities in the density of states of the TBG. Our study thus developed a route to identify the rotation angle of stacked bilayer graphene by means of a straightforward optical method, which can be further applied in other stacked van der Waals layered materials.

Charge State of Au Atoms on an Oxidized Rutile TiO2(110) Surface by AFM/KPFM at 78 K.

The charge state of noble metal atoms on a semiconductor surface is an important factor in surface catalysis. In this study, Au atoms were deposited on the rutile TiO2(110) surface to characterize its charge properties using atomic force microscopy with Kelvin probe force microscopy at 78 K. Au single atoms, dimers, and trimers at different sites on the surface were investigated. Positively charged Au atoms were verified at oxygen sites, while negatively charged Au atoms were found near oxygen vacancy sites. Furthermore, the charge states of small Au nanoclusters were clarified. Understanding the charge states of Au atoms is significant for identifying their efficient catalytic effects in surface catalysis.

Conversion of chirality to twisting via sequential one-dimensional and two-dimensional growth of graphene spirals.

The properties of two-dimensional (2D) van der Waals materials can be tuned through nanostructuring or controlled layer stacking, where interlayer hybridization induces exotic electronic states and transport phenomena. Here we describe a viable approach and underlying mechanism for the assisted self-assembly of twisted layer graphene. The process, which can be implemented in standard chemical vapour deposition growth, is best described by analogy to origami and kirigami with paper. It involves the controlled induction of wrinkle formation in single-layer graphene with subsequent wrinkle folding, tearing and re-growth. Inherent to the process is the formation of intertwined graphene spirals and conversion of the chiral angle of 1D wrinkles into a 2D twist angle of a 3D superlattice. The approach can be extended to other foldable 2D materials and facilitates the production of miniaturized electronic components, including capacitors, resistors, inductors and superconductors.

Electronic Janus lattice and kagome-like bands in coloring-triangular MoTe2 monolayers.

Polymorphic structures of transition metal dichalcogenides (TMDs) host exotic electronic states, like charge density wave and superconductivity. However, the number of these structures is limited by crystal symmetries, which poses a challenge to achieving tailored lattices and properties both theoretically and experimentally. Here, we report a coloring-triangle (CT) latticed MoTe2 monolayer, termed CT-MoTe2, constructed by controllably introducing uniform and ordered mirror-twin-boundaries into a pristine monolayer via molecular beam epitaxy. Low-temperature scanning tunneling microscopy and spectroscopy (STM/STS) together with theoretical calculations reveal that the monolayer has an electronic Janus lattice, i.e., an energy-dependent atomic-lattice and a Te pseudo-sublattice, and shares the identical geometry with the Mo5Te8 layer. Dirac-like and flat electronic bands inherently existing in the CT lattice are identified by two broad and two prominent peaks in STS spectra, respectively, and verified with density-functional-theory calculations. Two types of intrinsic domain boundaries were observed, one of which maintains the electronic-Janus-lattice feature, implying potential applications as an energy-tunable electron-tunneling barrier in future functional devices.

Identification of a common ice nucleus on hydrophilic and hydrophobic close-packed metal surfaces.

Establishing a general model of heterogeneous ice nucleation has long been challenging because of the surface water structures found on different substrates. Identifying common water clusters, regardless of the underlying substrate, is one of the key steps toward solving this problem. Here, we demonstrate the presence of a common water cluster found on both hydrophilic Pt(111) and hydrophobic Cu(111) surfaces using scanning tunneling microscopy and non-contact atomic force microscopy. Water molecules self-assemble into a structure with a central flat-lying hexagon and three fused pentagonal rings, forming a cluster consisting of 15 individual water molecules. This cluster serves as a critical nucleus during ice nucleation on both surfaces: ice growth beyond this cluster bifurcates to form two-dimensional (three-dimensional) layers on hydrophilic (hydrophobic) surfaces. Our results reveal the inherent similarity and distinction at the initial stage of ice growth on hydrophilic and hydrophobic close-packed metal surfaces; thus, these observations provide initial evidence toward a general model for water-substrate interaction.

Discovery and construction of surface kagome electronic states induced by p-d electronic hybridization in Co3Sn2S2.

Kagome-lattice materials possess attractive properties for quantum computing applications, but their synthesis remains challenging. Herein, based on the compelling identification of the two cleavable surfaces of Co3Sn2S2, we show surface kagome electronic states (SKESs) on a Sn-terminated triangular Co3Sn2S2 surface. Such SKESs are imprinted by vertical p-d electronic hybridization between the surface Sn (subsurface S) atoms and the buried Co kagome-lattice network in the Co3Sn layer under the surface. Owing to the subsequent lateral hybridization of the Sn and S atoms in a corner-sharing manner, the kagome symmetry and topological electronic properties of the Co3Sn layer is proximate to the Sn surface. The SKESs and both hybridizations were verified via qPlus non-contact atomic force microscopy (nc-AFM) and density functional theory calculations. The construction of SKESs with tunable properties can be achieved by the atomic substitution of surface Sn (subsurface S) with other group III-V elements (Se or Te), which was demonstrated theoretically. This work exhibits the powerful capacity of nc-AFM in characterizing localized topological states and reveals the strategy for synthesis of large-area transition-metal-based kagome-lattice materials using conventional surface deposition techniques.

Fe Single Atom Catalysts Promoting Polysulfide Redox Reduction in Quantum Dot Photovoltaics.

Developing cost-effective and highly efficient photocathodes toward polysulfide redox reduction is highly desirable for advanced quantum dot (QD) photovoltaics. Herein, we demonstrate nitrogen doped carbon (N-C) shell-supported iron single atom catalysts (Fe-SACs) capable of catalyzing polysulfide reduction in QD photovoltaics for the first time. Specifically, Fe-SACs with FeN4 active sites feature a power conversion efficiency of 13.7% for ZnCuInSe-QD photovoltaics (AM1.5G, 100 mW/cm2), which is the highest value for ZnCuInSe QD-based photovoltaics, outperforming those of Cu-SACs and N-C catalysts. Compared with N-C, Fe-SACs exhibit suitable energy level matching with polysulfide redox couples, revealed by the Kelvin probe force microscope, which accelerates the charge transferring at the interfaces of catalyst/polysulfide redox couple. Density functional theory calculations demonstrate that the outstanding catalytic activity of Fe-SACs originates from the preferable adsorption of S42- on the FeN4 active sites and the high activation degree of the S-S bonds in S42- initiated by the FeN4 active sites.

Controllable CVD Growth of 2D Cr5Te8 Nanosheets with Thickness-Dependent Magnetic Domains.

As a unique 2D magnetic material with self-intercalated structure, Cr5Te8 exhibits many intriguing magnetic properties. While its ferromagnetism of Cr5Te8 has been previously reported, the research on its magnetic domain remains unexplored. Herein, we have successfully fabricated 2D Cr5Te8 nanosheets with controlled thickness and lateral size by chemical vapor deposition (CVD). Then magnetic property measurement system revealed Cr5Te8 nanosheets exhibiting intense out-of-plane ferromagnetism with a Curie temperature (TC) of 176 K. Significantly, we reported for the first time two magnetic domains: magnetic bubbles and thickness-dependent maze-like magnetic domains in our Cr5Te8 nanosheets by cryogenic magnetic force microscopy (MFM). The domain width of the maze-like magnetic domains increases rapidly with decreasing sample thickness; meanwhile, the domain contrast decreases. This indicates the dominant role of ferromagnetism shifts from dipolar interactions to magnetic anisotropy. Our research not only establishes a pathway for the controllable growth of 2D magnetic materials but also points toward novel avenues for regulating magnetic phases and methodically tuning domain characteristics.

A natural indirect-to-direct band gap transition in artificially fabricated MoS2 and MoSe2 flowers.

Twisted bilayer (tB) transition metal dichalcogenide (TMD) structures formed from two pieces of a periodic pattern overlaid with a relative twist manifest novel electronic and optical properties and correlated electronic phenomena. Here, twisted flower-like MoS2 and MoSe2 bilayers were artificially fabricated by the chemical vapor deposition (CVD) method. Photoluminescence (PL) studies demonstrated that an energy band structural transition from the indirect gap to the direct gap happened in the region away from the flower center in tB MoS2 (MoSe2) flower patterns, accompanied by an enhanced PL intensity. The indirect-to-direct-gap transition in the tB-MoS2 (MoSe2) flower dominantly originated from a gradually enlarged interlayer spacing and thus, interlayer decoupling during the spiral growth of tB flower patterns. Meanwhile, the expanded interlayer spacing resulted in a decreased effective mass of the electrons. This means that the charged exciton (trion) population was reduced and the neutral exciton density was increased to obtain the upgraded PL intensity in the off-center region. Our experimental results were further evidenced by the density functional theory (DFT) calculations of the energy band structures and the effective masses of electrons and holes for the artificial tB-MoS2 flower with different interlayer spacings. The single-layer behavior of tB flower-like homobilayers provided a viable route to finely manipulate the energy band gap and the corresponding exotic optical properties by locally tuning the stacked structures and to satisfy the real requirement in TMD-based optoelectronic devices.

Twist angle-dependent work functions in CVD-grown twisted bilayer graphene probed by Kelvin probe force microscopy.

Tailoring the interlayer twist angle of bilayer graphene (BLG) significantly affects its electronic properties, including its superconductivity, topological transitions, ferromagnetic states, and correlated insulating states. These exotic electronic properties are sensitive to the work functions of BLG samples. In this study, the twist angle-dependent work functions of chemical vapour deposition-grown twisted bilayer graphene (tBLG) were investigated in detail using Kelvin probe force microscopy (KPFM) in combination with Raman spectroscopy. The thickness-dependent surface potentials of Bernal-stacked multilayer graphene were measured. It is found that with the increase in the number of layers, the work function decreases and tends to saturate. Bernal-stacked BLG and tBLG were determined via KPFM due to their twist angle-specific surface potentials. The detailed relationship between the twist angle and surface potential was determined via in situ KPFM and Raman spectral measurements. With the increase in the twist angle, the work function of tBLG will increase rapidly and then increase slowly when it is greater than 5°. The thermal stability of tBLG was investigated through a controlled annealing process. tBLG will become Bernal-stacked BLG after annealing at 350 °C. Our work provides the twist angle-dependent surface potentials of tBLG and provides the relevant conditions for the stability of the twist angle, which lays the foundation for further exploration of its twist angle-dependent electronic properties.

Electrical and magnetic anisotropies in van der Waals multiferroic CuCrP2S6.

Multiferroic materials have great potential in non-volatile devices for low-power and ultra-high density information storage, owing to their unique characteristic of coexisting ferroelectric and ferromagnetic orders. The effective manipulation of their intrinsic anisotropy makes it promising to control multiple degrees of the storage "medium". Here, we have discovered intriguing in-plane electrical and magnetic anisotropies in van der Waals (vdW) multiferroic CuCrP2S6. The uniaxial anisotropies of current rectifications, magnetic properties and magnon modes are demonstrated and manipulated by electric direction/polarity, temperature variation and magnetic field. More important, we have discovered the spin-flop transition corresponding to specific resonance modes, and determined the anisotropy parameters by consistent model fittings and theoretical calculations. Our work provides in-depth investigation and quantitative analysis of electrical and magnetic anisotropies with the same easy axis in vdW multiferroics, which will stimulate potential device applications of artificial bionic synapses, multi-terminal spintronic chips and magnetoelectric devices.

Effect of Al modification on the adsorption of As2O3 on the CaSiO3(001) surface: A DFT study.

CaSiO3 is highly resistant to sintering and can trap arsenic at high temperatures in the boiler furnace. However, the trapping capacity of CaSiO3 for arsenic does not meet the requirements of practical applications, and it is easy to react with acidic gases, which significantly affects the adsorptive property of arsenic. In this paper, the effect of Al modification on the As2O3 adsorption behaviour on the CaSiO3(001) surface was systematically investigated using a density functional theory. By comparing the magnitude of adsorption energy of different sites, the active site of As2O3 adsorbed on the surface of CaSiO3(001) was determined to be Ca, and the adsorption activity of As2O3 by the silicon oxygen chain composed of [SiO4] tetrahedron is deficient. The Si atoms in the [SiO4] tetrahedral structure are directly replaced by Al atoms, the difference in bond length and bond energy between Al-O bond and Si-O bond is used to promote the redistribution of surface charge and the increase of local structural bond angle of CaSiO3(001), leading to the exposure of new active sites (Si-top and Al-top sites) on the silicon oxygen chain. The new active site can realize the chemical adsorption of As2O3, the higher adsorption energy of the Al-top site is attributed to the stronger s-p orbital hybridization between Al and O atoms after doping, which is more conducive to the charge transfer between As2O3 and the adsorbent surface. In this work, influence of SO2 and HCl gases on the adsorption of As2O3 by modified silicon oxygen chains was also discussed. The results show that SO2 and HCl in the flue gas may occupy the Al-top site on the silicon oxygen chain through chemical adsorption, and reduce the activity of this site, thereby affecting the adsorption of As2O3. However, the exposed Si-top sites owing to Al doping show good acidic gas resistance, which in turn help the surface of Al-CaSiO3(001) can also maintain stable adsorption of As2O3 in SO2 and HCl atmosphere.

Selective activation of four quasi-equivalent C-H bonds yields N-doped graphene nanoribbons with partial corannulene motifs.

Selective C-H bond activation is one of the most challenging topics for organic reactions. The difficulties arise not only from the high C-H bond dissociation enthalpies but also the existence of multiple equivalent/quasi-equivalent reaction sites in organic molecules. Here, we successfully achieve the selective activation of four quasi-equivalent C-H bonds in a specially designed nitrogen-containing polycyclic hydrocarbon (N-PH). Density functional theory calculations reveal that the adsorption of N-PH on Ag(100) differentiates the activity of the four ortho C(sp3) atoms in the N-heterocycles into two groups, suggesting a selective dehydrogenation, which is demonstrated by sequential-annealing experiments of N-PH/Ag(100). Further annealing leads to the formation of N-doped graphene nanoribbons with partial corannulene motifs, realized by the C-H bond activation process. Our work provides a route of designing precursor molecules with ortho C(sp3) atom in an N-heterocycle to realize surface-induced selective dehydrogenation in quasi-equivalent sites.

Direct growth of hBN/Graphene heterostructure via surface deposition and segregation for independent thickness regulation.

Hexagonal boron nitride/graphene (hBN/G) vertical heterostructures have attracted extensive attention, owing to the unusual physical properties for basic research and electronic device applications. Here we report a facile deposition-segregation technique to synthesize hBN/G heterostructures on recyclable platinum (Pt) foil via low pressure chemical vapor deposition. The growth mechanism of the vertical hBN/G is demonstrated to be the surface deposition of hBN on top of the graphene segregated from the Pt foil with pre-dissolved carbon. The thickness of hBN and graphene can be controlled separately from sub-monolayer to multilayer through the fine control of the growth parameters. Further investigations by Raman, scanning Kelvin probe microscopy and transmission electron microscope show that the hBN/G inclines to form a heterostructure with strong interlayer coupling and with interlayer twist angle smaller than 1.5°. This deposition-segregation approach paves a new pathway for large-scale production of hBN/G heterostructures and could be applied to synthesize of other van der Waals heterostructures.

Low-Temperature Synthesis of Boron Nitride as a Large-Scale Passivation and Protection Layer for Two-Dimensional Materials and High-Performance Devices.

Two-dimensional materials (2DMs) with extraordinary electronic and optical properties have attracted great interest in optoelectronic applications. Due to their atomically thin feature, 2DM-based devices are generally sensitive to oxygen and moisture in ambient air, and thus, practical application of durable 2DM-based devices remains challenging. Here, we report a novel strategy to directly synthesize amorphous BN film on various 2DMs and field-effect transistor (FET) devices at low temperatures by conventional chemical vapor deposition. The wafer-scale BN film with controllable thickness serves as a passivation and heat dissipation layer, further improving the long-term stability, the resistance to laser irradiation, and the antioxidation performance of the underneath 2DMs. In particular, the BN capping layer could be deposited directly on a WSe2 FET at low temperature to achieve a clean and conformal interface. The high performance of the BN-capped WSe2 device is realized with suppressed current fluctuations and 10-fold enhanced carrier mobility. The transfer-free amorphous BN synthesis technique is simple and applicable to various 2DMs grown on arbitrary substrates, which shows great potential for applications in future two-dimensional electronics.

Vanadium-Doped Molybdenum Diselenide Atomic Layers with Room-Temperature Ferromagnetism.

Diluted two-dimensional magnetic semiconductors with high Curie temperature are highly sought after because of their potential applications in spintronics. Development of new techniques for preparation of high quality diluted magnetic semiconductors is critical for their applications. In this study, vanadium-doped molybdenum selenide, a new diluted magnetic semiconductor, was synthesized by a single-step chemical vapor deposition method. The merit of this method is that the molybdenum and vanadium precursors can be supplied to the growth substrate uniformly. Photoluminescence measurements reveal that the band gap of MoSe2 decreases after doping, which can be attributed to the formation of impurity energy band caused by p-type doping at the valence band maximum. Thus, the V-doped MoSe2 still maintains the semiconducting characteristics. Vibrating sample magnetometer studies clearly show the ferromagnetism of V-doped MoSe2 at room temperature. DFT calculations illustrates the joint contribution of V dopants and nearby atoms to the magnetic moments. This study provides future prospects for the multifunctional application of two-dimensional materials.

An all two-dimensional vertical heterostructure graphene/CuInP2S6/MoS2for negative capacitance field effect transistor.

As scaling down the size of metal oxide semiconductor field-effect transistors (FETs), power dissipation has become a major challenge. Lowering down the sub-threshold swing (SS) is known as an effective technique to decrease the operating voltage of FETs and hence lower down the power consumption. However, the Boltzmann distribution of electrons (so-called 'Boltzmann tyranny') implements a physical limit to the SS value. Use of negative capacitance (NC) effect has enabled a new path to achieve a low SS below the Boltzmann limit (60 mV dec-1at room temperature). In this work, we have demonstrated a NC-FET from an all two-dimensional (2D) metal ferroelectric semiconductor (MFS) vertical heterostructure: Graphene/CuInP2S6/MoS2. The negative capacitance from the ferroelectric CuInP2S6has enabled the breaking of the 'Boltzmann tyranny'. The heterostructure based device has shown steep slopes switching below 60 mV dec-1(lowest to < 10 mV dec-1) over 3 orders of source-drain current, which provides an avenue for all 2D material based steep slope FETs.

NBN-Doped Bis-Tetracene and Peri-Tetracene: Synthesis and Characterization.

Combining solution-based and surface-assisted synthesis, we demonstrate the first synthesis of NBN-doped bis-tetracene (NBN-BT) and peri-tetracene (NBN-PT). The chemical structures are clearly elucidated by high-resolution scanning tunneling microscopy (STM) in combination with noncontact atomic force microscopy (nc-AFM). Scanning tunneling spectroscopy (STS) characterizations reveal that NBN-BT and NBN-PT possess higher energy gaps than bis-tetracene and peri-tetracene. Interestingly, NBN-BT can undergo stepwise one-electron oxidation and convert into its corresponding radical cation and then to its dication. The energy gap of the NBN-BT dication is similar to that of bis-tetracene, indicating their isoelectronic relationship. Moreover, a similar energy gap between the NBN-PT dication and peri-tetracene can be predicted by DFT calculations. This work provides a novel synthesis along with characterizations of multi-NBN-doped zigzag-edged peri-acenes with tunable electronic properties.

Size-dependent strain-engineered nanostructures in MoS2monolayer investigated by atomic force microscopy.

The strain has been employed for controlled modification of electronical and mechanical properties of two-dimensional (2D) materials. However, the thermal strain-engineered behaviors of the CVD-grown MoS2have not been systematically explored. Here, we investigated the strain-induced structure and properties of CVD-grown triangular MoS2flakes by several advanced atomic force microscopy. Two different kinds of flakes with sharp-corner or vein-like nanostructures are experimentally discovered due to the size-dependent strain behaviors. The critical size of these two kinds of flakes can be roughly estimated at âˆ¼17µm. Within the small flakes, the sharp-corner regions show specific strain-modified properties due to the suffering of large tensile strain. While in the large MoS2flakes, the complicated vein-like nanoripple structures were formed due to the interface slipping process under the larger tensile strain. Our work not only demonstrates the size-specific strain behaviors of MoS2flakes but also sheds light on the artificial design and preparation of strain-engineered nanostructures for the devices based on the 2D materials.