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.

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.

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.

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.

Graphene Nanoribbon Grids of Sub-10 nm Widths with High Electrical Connectivity.

Quasi-one-dimensional (1D) graphene nanoribbons (GNRs) have finite band gaps and active edge states and therefore can be useful for advanced chemical and electronic devices. Here, we present the formation of GNR grids via seed-assisted chemical vapor deposition on Ge(100) substrates. Nucleation seeds, provided by unzipped C60, initiated growth of the GNRs. The GNRs grew toward two orthogonal directions in an anisotropic manner, templated by the single crystalline substrate, thereby forming grids that had lateral stitching over centimeter scales. The spatially uniform grid can be transferred and patterned for batch fabrication of devices. The GNR grids showed percolative conduction with a high electrical sheet conductance of ∼2 µS·sq and field-effect mobility of ∼5 cm2/(V·s) in the macroscopic channels, which confirm excellent lateral stitching between domains. From transconductance measurements, the intrinsic band gap of GNRs with sub-10 nm widths was estimated as ∼80 meV, similar to theoretical expectation. Our method presents a scalable way to fabricate atomically thin elements with 1D characteristics for integration with various nanodevices.

Direct Synthesis of Molybdenum Phosphide Nanorods on Silicon Using Graphene at the Heterointerface for Efficient Photoelectrochemical Water Reduction.

HIGHLIGHTS: MoP nanorod-array catalysts were directly synthesized on graphene passivated silicon photocathodes without secondary phase. Mo-O-C covalent bondings and energy band bending at heterointerfaces facilitate the electron transfer to the reaction sites. Numerous catalytic sites and drastically enhanced anti-reflectance of MoP nanorods contribute to the high solar energy conversion efficiency. Transition metal phosphides (TMPs) and transition metal dichalcogenides (TMDs) have been widely investigated as photoelectrochemical (PEC) catalysts for hydrogen evolution reaction (HER). Using high-temperature processes to get crystallized compounds with large-area uniformity, it is still challenging to directly synthesize these catalysts on silicon photocathodes due to chemical incompatibility at the heterointerface. Here, a graphene interlayer is applied between p-Si and MoP nanorods to enable fully engineered interfaces without forming a metallic secondary compound that absorbs a parasitic light and provides an inefficient electron path for hydrogen evolution. Furthermore, the graphene facilitates the photogenerated electrons to rapidly transfer by creating Mo-O-C covalent bondings and energetically favorable band bending. With a bridging role of graphene, numerous active sites and anti-reflectance of MoP nanorods lead to significantly improved PEC-HER performance with a high photocurrent density of 21.8 mA cm-2 at 0 V versus RHE and high stability. Besides, low dependence on pH and temperature is observed with MoP nanorods incorporated photocathodes, which is desirable for practical use as a part of PEC cells. These results indicate that the direct synthesis of TMPs and TMDs enabled by graphene interlayer is a new promising way to fabricate Si-based photocathodes with high-quality interfaces and superior HER performance.

Pristine Graphene Insertion at the Metal/Semiconductor Interface to Minimize Metal-Induced Gap States.

Metal (M) contact with a semiconductor (S) introduces metal-induced gap states (MIGS), which makes it difficult to study the intrinsic electrical properties of S. A bilayer of metal with graphene (Gr), i.e., a M/Gr bilayer, may form a contact with S to minimize MIGS. However, it has been challenging to realize the pristine M/Gr/S junctions without interfacial contaminants, which result in additional interfacial states. Here, we successfully demonstrate the atomically clean M/Gr/n-type silicon (Si) junctions via all-dry transfer of M/Gr bilayers onto Si. The fabricated M/Gr/Si junctions significantly increase the current density J at reverse bias, compared to those of M/Si junctions without a Gr interlayer (e.g., by 105 times for M = Au in Si(111)). The increase of the reverse J by a Gr interlayer is more prominent in Si(111) than in Si(100), whereas in M/Si junctions, J is independent of the type of Si surface. The different transport data between M/Gr/Si(111) and M/Gr/Si(100) are consistent with Fermi-level pinning by different surface states of Si(111) and Si(100). Our findings suggest the effective way to suppress MIGS by an introduction of the clean Gr interlayer, which paves the way to study intrinsic electrical properties of various materials.

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.

A Novel Surface Modification and Immobilization Method of Anti-CD25 Antibody on Nonwoven Fabric Filter Removing Regulatory T Cells Selectively.

Anti-CD25 antibodies were immobilized on polypropylene (PP) nonwoven fabrics to specifically remove mouse regulatory T cells (Tregs) from mouse spleen cells. PP fibers were coated with peptide nanosheets, which were prepared by self-assembling of a mixture of X-poly(sarcosine)-b-(l-Leu-Aib)6 (X: glycolic acid or a phenylboronic acid) and Y-poly(sarcosine)-b-(d-Leu-Aib)6 (Y: glycolic acid or diazirine derivative). Anti-CD25 antibodies were immobilized by covalent linking between the sugar moiety of the antibody and the phenylboronic acid group on the peptide nanosheet. The removal rate of mouse Tregs from the mouse spleen cells was more than 95% only by passing the filters, while the nonspecific removal rates of other cells were less than 15%. The coating of peptide nanosheets on PP fibers was very effective to provide a suitable environment for the immobilized antibody to interact with the counterpart cells while the coating suppressed nonspecific adsorption of other cells.

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.

Stacking angle-tunable photoluminescence from interlayer exciton states in twisted bilayer graphene.

Twisted bilayer graphene (tBLG) is a metallic material with two degenerate van Hove singularity transitions that can rehybridize to form interlayer exciton states. Here we report photoluminescence (PL) emission from tBLG after resonant 2-photon excitation, which tunes with the interlayer stacking angle, θ. We spatially image individual tBLG domains at room-temperature and show a five-fold resonant PL-enhancement over the background hot-electron emission. Prior theory predicts that interlayer orbitals mix to create 2-photon-accessible strongly-bound (~0.7 eV) exciton and continuum-edge states, which we observe as two spectral peaks in both PL excitation and excited-state absorption spectra. This peak splitting provides independent estimates of the exciton binding energy which scales from 0.5-0.7 eV with θ = 7.5° to 16.5°. A predicted vanishing exciton-continuum coupling strength helps explain both the weak resonant PL and the slower 1 ps-1 exciton relaxation rate observed. This hybrid metal-exciton behavior electron thermalization and PL emission are tunable with stacking angle for potential enhancements in optoelectronic and fast-photosensing graphene-based applications.

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.

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.

Atomically Thin Ohmic Edge Contacts Between Two-Dimensional Materials.

With the decrease of the dimensions of electronic devices, the role played by electrical contacts is ever increasing, eventually coming to dominate the overall device volume and total resistance. This is especially problematic for monolayers of semiconducting transition-metal dichalcogenides (TMDs), which are promising candidates for atomically thin electronics. Ideal electrical contacts to them would require the use of similarly thin electrode materials while maintaining low contact resistances. Here we report a scalable method to fabricate ohmic graphene edge contacts to two representative monolayer TMDs, MoS2 and WS2. The graphene and TMD layer are laterally connected with wafer-scale homogeneity, no observable overlap or gap, and a low average contact resistance of 30 kΩ·µm. The resulting graphene edge contacts show linear current-voltage (I-V) characteristics at room temperature, with ohmic behavior maintained down to liquid helium temperatures.

Chiral atomically thin films.

Chiral materials possess left- and right-handed counterparts linked by mirror symmetry. These materials are useful for advanced applications in polarization optics, stereochemistry and spintronics. In particular, the realization of spatially uniform chiral films with atomic-scale control of their handedness could provide a powerful means for developing nanodevices with novel chiral properties. However, previous approaches based on natural or grown films, or arrays of fabricated building blocks, could not offer a direct means to program intrinsic chiral properties of the film on the atomic scale. Here, we report a chiral stacking approach, where two-dimensional materials are positioned layer-by-layer with precise control of the interlayer rotation (θ) and polarity, resulting in tunable chiral properties of the final stack. Using this method, we produce left- and right-handed bilayer graphene, that is, a two-atom-thick chiral film. The film displays one of the highest intrinsic ellipticity values (6.5 deg µm(-1)) ever reported, and a remarkably strong circular dichroism (CD) with the peak energy and sign tuned by θ and polarity. We show that these chiral properties originate from the large in-plane magnetic moment associated with the interlayer optical transition. Furthermore, we show that we can program the chiral properties of atomically thin films layer-by-layer by producing three-layer graphene films with structurally controlled CD spectra.