Dephasing Dynamics Accessed by High Harmonic Generation: Determination of Electron-Hole Decoherence of Dirac Fermions.

We reveal the critical effect of ultrashort dephasing on the polarization of high harmonic generation in Dirac fermions. As the elliptically polarized laser pulse falls in or slightly beyond the multiphoton regime, the elliptically polarized high harmonic generation is produced and exhibits a characteristic polarimetry of the polarization ellipse, which is found to depend on the decoherence time T2. T2 could then be determined to be a few femtoseconds directly from the experimentally observed polarimetry of high harmonics. This shows a sharp contrast with the semimetal regime of higher pump intensity, where the polarimetry is irrelevant to T2. An access to the dephasing dynamics would extend the prospect of high harmonic generation into the metrology of a femtosecond dynamic process in the coherent quantum control.

Thermodynamically Driven Tilt Grain Boundaries of Monolayer Crystals Using Catalytic Liquid Alloys.

We report a method to precisely control the atomic defects at grain boundaries (GBs) of monolayer MoS2 by vapor-liquid-solid (VLS) growth using sodium molybdate liquid alloys, which serve as growth catalysts to guide the formations of the thermodynamically most stable GB structure. The Mo-rich chemical environment of the alloys results in Mo-polar 5|7 defects with a yield exceeding 95%. The photoluminescence (PL) intensity of VLS-grown polycrystalline MoS2 films markedly exceeds that of the films, exhibiting abundant S 5|7 defects, which are kinetically driven by vapor-solid-solid growths. Density functional theory calculations indicate that the enhanced PL intensity is due to the suppression of nonradiative recombination of charged excitons with donor-type defects of adsorbed Na elements on S 5|7 defects. Catalytic liquid alloys can aid in determining a type of atomic defect even in various polycrystalline 2D films, which accordingly provides a technical clue to engineer their properties.

Wafer-Scale Programmed Assembly of One-Atom-Thick Crystals.

Crystalline films offer various physical properties based on the modulation of their thicknesses and atomic structures. The layer-by-layer assembly of atomically thin crystals provides a powerful means to arbitrarily design films at the atomic level, which are unattainable with existing growth technologies. However, atomically clean assembly of the materials with high scalability and reproducibility remains challenging. We report programmed crystal assembly of graphene and monolayer hexagonal boron nitride, assisted by van der Waals interactions, to form wafer-scale films of pristine interfaces with near-unity yield. The atomic configurations of the films are tailored with layer-resolved compositions and in-plane crystalline orientations. We demonstrate batch-fabricated tunnel device arrays with modulation of the resistance over orders of magnitude by thickness control of the hexagonal boron nitride barrier with single-atom precision and large-scale, twisted multilayer graphene with programmable electronic band structures and crystal symmetries. Our results constitute an important development in the artificial design of large-scale films.

High-mobility three-atom-thick semiconducting films with wafer-scale homogeneity.

The large-scale growth of semiconducting thin films forms the basis of modern electronics and optoelectronics. A decrease in film thickness to the ultimate limit of the atomic, sub-nanometre length scale, a difficult limit for traditional semiconductors (such as Si and GaAs), would bring wide benefits for applications in ultrathin and flexible electronics, photovoltaics and display technology. For this, transition-metal dichalcogenides (TMDs), which can form stable three-atom-thick monolayers, provide ideal semiconducting materials with high electrical carrier mobility, and their large-scale growth on insulating substrates would enable the batch fabrication of atomically thin high-performance transistors and photodetectors on a technologically relevant scale without film transfer. In addition, their unique electronic band structures provide novel ways of enhancing the functionalities of such devices, including the large excitonic effect, bandgap modulation, indirect-to-direct bandgap transition, piezoelectricity and valleytronics. However, the large-scale growth of monolayer TMD films with spatial homogeneity and high electrical performance remains an unsolved challenge. Here we report the preparation of high-mobility 4-inch wafer-scale films of monolayer molybdenum disulphide (MoS2) and tungsten disulphide, grown directly on insulating SiO2 substrates, with excellent spatial homogeneity over the entire films. They are grown with a newly developed, metal-organic chemical vapour deposition technique, and show high electrical performance, including an electron mobility of 30 cm(2) V(-1) s(-1) at room temperature and 114 cm(2) V(-1) s(-1) at 90 K for MoS2, with little dependence on position or channel length. With the use of these films we successfully demonstrate the wafer-scale batch fabrication of high-performance monolayer MoS2 field-effect transistors with a 99% device yield and the multi-level fabrication of vertically stacked transistor devices for three-dimensional circuitry. Our work is a step towards the realization of atomically thin integrated circuitry.

Metal Nanoparticle Exsolution on a Perovskite Stannate Support with High Electrical Conductivity.

In situ exsolution of metal nanoparticles (NPs) is emerging as an alternative technique to deliver thermally stable and evenly dispersed metal NPs, which exhibit excellent adhesion with conducting perovskite oxide supports. Here we provide the first demonstration that Ni metal NPs with high areal density (∼175 µm-2) and fine size (∼38.65 nm) are exsolved from an A-site-deficient perovskite stannate support (La0.2Ba0.7Sn0.9Ni0.1O3-δ (LBSNO)). The NPs are strongly anchored and impart coking resistance, and the Ni-exsolved stannates show exceptionally high electrical conductivity (∼700 S·cm-1). The excellent conductivity is attributed to conduction between delocalized Sn 5s orbitals along with structural improvement toward ABO3 stoichiometry in the stannate support. We also reveal that experimental conditions with strong interaction must be optimized to obtain Ni exsolution without degrading the perovskite stannate framework. Our finding suggests a unique process to induce the formation of metal NPs embedded in stannate with excellent electrical properties.

All-Dry Transfer of Graphene Film by van der Waals Interactions.

We report a method that uses van der Waals interactions to transfer continuous, high-quality graphene films from Ge(110) to a different substrate held by hexagonal boron nitride carriers in a clean, dry environment. The transferred films are uniform and continuous with low defect density and few charge puddles. The transfer is effective because of the weak interfacial adhesion energy between graphene and Ge. Based on the minimum strain energy required for the isolation of film, the upper limit of the interfacial adhesion energy is estimated to be 23 meV per carbon atom, which makes graphene/Ge(110) the first as-grown graphene film that has a substrate adhesion energy lower than that of typical van der Waals interactions between layered materials. Our results suggest that graphene on Ge can serve as an ideal material platform to be integrated with other material systems by a clean assembly process.

Graphene and boron nitride lateral heterostructures for atomically thin circuitry.

Precise spatial control over the electrical properties of thin films is the key capability enabling the production of modern integrated circuitry. Although recent advances in chemical vapour deposition methods have enabled the large-scale production of both intrinsic and doped graphene, as well as hexagonal boron nitride (h-BN), controlled fabrication of lateral heterostructures in these truly atomically thin systems has not been achieved. Graphene/h-BN interfaces are of particular interest, because it is known that areas of different atomic compositions may coexist within continuous atomically thin films and that, with proper control, the bandgap and magnetic properties can be precisely engineered. However, previously reported approaches for controlling these interfaces have fundamental limitations and cannot be easily integrated with conventional lithography. Here we report a versatile and scalable process, which we call 'patterned regrowth', that allows for the spatially controlled synthesis of lateral junctions between electrically conductive graphene and insulating h-BN, as well as between intrinsic and substitutionally doped graphene. We demonstrate that the resulting films form mechanically continuous sheets across these heterojunctions. Conductance measurements confirm laterally insulating behaviour for h-BN regions, while the electrical behaviour of both doped and undoped graphene sheets maintain excellent properties, with low sheet resistances and high carrier mobilities. Our results represent an important step towards developing atomically thin integrated circuitry and enable the fabrication of electrically isolated active and passive elements embedded in continuous, one-atom-thick sheets, which could be manipulated and stacked to form complex devices at the ultimate thickness limit.

Tuning the Viscoelasticity of Peptide Vesicles by Adjusting Hydrophobic Helical Blocks Comprising Amphiphilic Polypeptides.

Amphiphilic block polypeptides of poly(sarcosine)-b-(l-Val-Aib)6 and poly(sarcosine)-b-(l-Leu-Aib)6 and their stereoisomers were self-assembled in water. Three kinds of binary systems of poly(sarcosine)-b-(l-Leu-Aib)6 with poly(sarcosine)-b-poly(d-Leu-Aib)6, poly(sarcosine)-b-poly(l-Val-Aib)6, or poly(sarcosine)-b-(d-Val-Aib)6 generated vesicles of ca. 200 nm diameter. The viscoelasticity of the vesicle membranes was evaluated by the nanoindentation method using AFM in water. The elasticity of the poly(sarcosine)-b-(l-Leu-Aib)6/poly(sarcosine)-b-poly(d-Leu-Aib)6 vesicle was 11-fold higher than that of the egg yolk liposome but decreased in combinations of the Leu- and Val-based amphiphilic polypeptides. The membrane elasticity is found to be adjustable by a suitable combination of helical blocks in terms of stereocomplex formation and the interdigitation of side chains among helices in the molecular assemblies.

Modulation of immunogenicity of poly(sarcosine) displayed on various nanoparticle surfaces due to different physical properties.

Poly(sarcosine) displayed on polymeric micelle is reported to trigger a T cell-independent type2 reaction with B1a cells in the mice to produce IgM and IgG3 antibodies. In addition to polymeric micelle, three kinds of vesicles displaying poly(sarcosine) on surface were prepared here to evaluate the amounts and avidities of IgM and IgG3, which were produced in mice, to correlate them with physical properties of the molecular assemblies. The largest amount of IgM was produced after twice administrations of a polymeric micelle of 35 nm diameter (G1). On the other hand, the production amount of IgG3 became the largest after twice administrations of G3 (vesicle of 229 nm diameter) or G4 (vesicle of 85 nm diameter). The augmented avidity of IgG3 after the twice administrations compared with that at the single administration was the highest with G3. These differences in immune responses are discussed in terms of surface density of poly(sarcosine) chains, nanoparticle size, hydrophobic component of poly(L-lactic acid) or (Leu- or Val-Aib)n , and membrane elasticity of the nanoparticles. Copyright © 2017 European Peptide Society and John Wiley & Sons, Ltd.

Polycrystalline graphene with single crystalline electronic structure.

We report the scalable growth of aligned graphene and hexagonal boron nitride on commercial copper foils, where each film originates from multiple nucleations yet exhibits a single orientation. Thorough characterization of our graphene reveals uniform crystallographic and electronic structures on length scales ranging from nanometers to tens of centimeters. As we demonstrate with artificial twisted graphene bilayers, these inexpensive and versatile films are ideal building blocks for large-scale layered heterostructures with angle-tunable optoelectronic properties.

Suppressive immune response of poly-(sarcosine) chains in peptide-nanosheets in contrast to polymeric micelles.

Nanoparticles are expected to be applicable for the theranostics as a carrier of the diagnostic and therapeutic agents. Lactosome is a polymeric micelle composed of amphiphilic polydepsipeptide, poly(sarcosine)64-block-poly(L-lactic acid)30, which was found to accumulate in solid tumors through the enhanced permeability and retention effect. However, lactosome was captured by liver on the second administration to a mouse. This phenomenon is called as the accelerated blood clearance phenomenon. On the other hand, peptide-nanosheet composed of amphiphilic polypeptide, poly(sarcosine)60-block-(L-Leu-Aib)6, where the poly(L-lactic acid) block in lactosome was replaced with the (L-Leu-Aib)6 block, abolished the accelerated blood clearance phenomenon. The ELISA and in vivo near-infrared fluorescence imaging revealed that peptide-nanosheets did not activate the immune system despite the same hydrophilic block being used. The high surface density of poly(sarcosine) chains on the peptide-nanosheet may be one of the causes of the suppressive immune response.

Stacking order dependent second harmonic generation and topological defects in h-BN bilayers.

The ability to control the stacking structure in layered materials could provide an exciting approach to tuning their optical and electronic properties. Because of the lower symmetry of each constituent monolayer, hexagonal boron nitride (h-BN) allows more structural variations in multiple layers than graphene; however, the structure-property relationships in this system remain largely unexplored. Here, we report a strong correlation between the interlayer stacking structures and optical and topological properties in chemically grown h-BN bilayers, measured mainly by using dark-field transmission electron microscopy (DF-TEM) and optical second harmonic generation (SHG) mapping. Our data show that there exist two distinct h-BN bilayer structures with different interlayer symmetries that give rise to a distinct difference in their SHG intensities. In particular, the SHG signal in h-BN bilayers is observed only for structures with broken inversion symmetry, with an intensity much larger than that of single layer h-BN. In addition, our DF-TEM data identify the formation of interlayer topological defects in h-BN bilayers, likely induced by local strain, whose properties are determined by the interlayer symmetry and the different interlayer potential landscapes.

Hyperspectral imaging of structure and composition in atomically thin heterostructures.

Precise vertical stacking and lateral stitching of two-dimensional (2D) materials, such as graphene and hexagonal boron nitride (h-BN), can be used to create ultrathin heterostructures with complex functionalities, but this diversity of behaviors also makes these new materials difficult to characterize. We report a DUV-vis-NIR hyperspectral microscope that provides imaging and spectroscopy at energies of up to 6.2 eV, allowing comprehensive, all-optical mapping of chemical composition in graphene/h-BN lateral heterojunctions and interlayer rotations in twisted bilayer graphene (tBLG). With the addition of transmission electron microscopy, we obtain quantitative structure-property relationships, confirming the formation of interfaces in graphene/h-BN lateral heterojunctions that are abrupt on a micrometer scale, and a one-to-one relationship between twist angle and interlayer optical resonances in tBLG. Furthermore, we perform similar hyperspectral imaging of samples that are supported on a nontransparent silicon/SiO2 substrate, enabling facile fabrication of atomically thin heterostructure devices with known composition and structure.

Integrated 1D epitaxial mirror twin boundaries for ultrascaled 2D MoS2 field-effect transistors.

In atomically thin van der Waals materials, grain boundaries-the line defects between adjacent crystal grains with tilted in-plane rotations-are omnipresent. When the tilting angles are arbitrary, the grain boundaries form inhomogeneous sublattices, giving rise to local electronic states that are not controlled. Here we report on epitaxial realizations of deterministic MoS2 mirror twin boundaries (MTBs) at which two adjoining crystals are reflection mirroring by an exactly 60° rotation by position-controlled epitaxy. We showed that these epitaxial MTBs are one-dimensionally metallic to a circuit length scale. By utilizing the ultimate one-dimensional (1D) feature (width ~0.4 nm and length up to a few tens of micrometres), we incorporated the epitaxial MTBs as a 1D gate to build integrated two-dimensional field-effect transistors (FETs). The critical role of the 1D MTB gate was verified to scale the depletion channel length down to 3.9 nm, resulting in a substantially lowered channel off-current at lower gate voltages. With that, in both individual and array FETs, we demonstrated state-of-the-art performances for low-power logics. The 1D epitaxial MTB gates in this work suggest a novel synthetic pathway for the integration of two-dimensional FETs-that are immune to high gate capacitance-towards ultimate scaling.

Large electroabsorption susceptibility mediated by internal photoconductive gain in Ge nanowires.

Large spectral modulation in the photon-to-electron conversion near the absorption band-edge of a semiconductor by an applied electrical field can be a basis for efficient electro-optical modulators. This electro-absorption effect in Group IV semiconductors is, however, inherently weak, and this poses the technological challenges for their electro-photonic integration. Here we report unprecedentedly large electro-absorption susceptibility at the direct band-edge of intrinsic Ge nanowire (NW) photodetectors, which is strongly diameter-dependent. We provide evidence that the large spectral shift at the 1.55 µm wavelength, enhanced up to 20 times larger than Ge bulk crystals, is attributed to the internal Franz-Keldysh effect across the NW surface field of ~10(5) V/cm, mediated by the strong photoconductive gain. This classical size-effect operating at the nanometer scale is universal, regardless of the choice of materials, and thus suggests general implications for the monolithic integration of Group IV photonic circuits.

Engineering Grain Boundaries in Two-Dimensional Electronic Materials.

Engineering the boundary structures in 2D materials provides an unprecedented opportunity to program the physical properties of the materials with extensive tunability and realize innovative devices with advanced functionalities. However, structural engineering technology is still in its infancy, and creating artificial boundary structures with high reproducibility remains difficult. In this review, various emergent properties of 2D materials with different grain boundaries, and the current techniques to control the structures, are introduced. The remaining challenges for scalable and reproducible structure control and the outlook on the future directions of the related techniques are also discussed.

High-Performance Solution-Processed 2D P-Type WSe2 Transistors and Circuits through Molecular Doping.

Semiconducting ink based on 2D single-crystal flakes with dangling-bond-free surfaces enables the implementation of high-performance devices on form-free substrates by cost-effective and scalable printing processes. However, the lack of solution-processed p-type 2D semiconducting inks with high mobility is an obstacle to the development of complementary integrated circuits. Here, a versatile strategy of doping with Br2 is reported to enhance the hole mobility by orders of magnitude for p-type transistors with 2D layered materials. Br2 -doped WSe2 transistors show a field-effect hole mobility of more than 27 cm2  V-1  s-1 , and a high on/off current ratio of ≈107 , and exhibits excellent operational stability during the on-off switching, cycling, and bias stressing testing. Moreover, complementary inverters composed of patterned p-type WSe2 and n-type MoS2 layered films are demonstrated with an ultra-high gain of 1280 under a driving voltage (VDD ) of 7 V. This work unveils the high potential of solution-processed 2D semiconductors with low-temperature processability for flexible devices and monolithic circuitry.

Gate-tunable quantum pathways of high harmonic generation in graphene.

Under strong laser fields, electrons in solids radiate high-harmonic fields by travelling through quantum pathways in Bloch bands in the sub-laser-cycle timescales. Understanding these pathways in the momentum space through the high-harmonic radiation can enable an all-optical ultrafast probe to observe coherent lightwave-driven processes and measure electronic structures as recently demonstrated for semiconductors. However, such demonstration has been largely limited for semimetals because the absence of the bandgap hinders an experimental characterization of the exact pathways. In this study, by combining electrostatic control of chemical potentials with HHG measurement, we resolve quantum pathways of massless Dirac fermions in graphene under strong laser fields. Electrical modulation of HHG reveals quantum interference between the multi-photon interband excitation channels. As the light-matter interaction deviates beyond the perturbative regime, elliptically polarized laser fields efficiently drive massless Dirac fermions via an intricate coupling between the interband and intraband transitions, which is corroborated by our theoretical calculations. Our findings pave the way for strong-laser-field tomography of Dirac electrons in various quantum semimetals and their ultrafast electronics with a gate control.

Large Memory Window of van der Waals Heterostructure Devices Based on MOCVD-Grown 2D Layered Ge4 Se9.

Van der Waals (vdW) heterostructures have drawn much interest over the last decade owing to their absence of dangling bonds and their intriguing low-dimensional properties. The emergence of 2D materials has enabled the achievement of significant progress in both the discovery of physical phenomena and the realization of superior devices. In this work, the group IV metal chalcogenide 2D-layered Ge4 Se9 is introduced as a new selection of insulating vdW material. 2D-layered Ge4 Se9 is synthesized with a rectangular shape using the metalcorganic chemical vapor deposition system using a liquid germanium precursor at 240 °C. By stacking the Ge4 Se9 and MoS2 , vdW heterostructure devices are fabricated with a giant memory window of 129 V by sweeping back gate range of ±80 V. The gate-independent decay time reveals that the large hysteresis is induced by the interfacial charge transfer, which originates from the low band offset. Moreover, repeatable conductance changes are observed over the 2250 pulses with low non-linearity values of 0.26 and 0.95 for potentiation and depression curves, respectively. The energy consumption of the MoS2 /Ge4 Se9 device is about 15 fJ for operating energy and the learning accuracy of image classification reaches 88.3%, which further proves the great potential of artificial synapses.