Graphene oxide-polyamine preprogrammable nanoreactors with sensing capability for corrosion protection of materials.

Corrosion is one of the major issues for sustainable manufacturing globally. The annual global cost of corrosion is US$2.5 trillion (approximately 3.4% of the world's GDP). The traditional ways of corrosion protection (such as barriers or inhibiting) are either not very effective (in the case of barrier protection) or excessively expensive (inhibiting). Here, we demonstrate a concept of nanoreactors, which are able to controllably release or adsorb protons or hydroxides directly on corrosion sites, hence, selectively regulating the corrosion reactions. A single nanoreactor comprises a nanocompartment wrapped around by a pH-sensing membrane represented, respectively, by a halloysite nanotube and a graphene oxide/polyamine envelope. A nanoreactor response is determined by the change of a signaling pH on a given corrosion site. The nanoreactors are self-assembled and suitable for mass-line production. The concept creates sustainable technology for developing smart anticorrosion coatings, which are nontoxic, selective, and inexpensive.

Face-to-face transfer of wafer-scale graphene films.

Graphene has attracted worldwide interest since its experimental discovery, but the preparation of large-area, continuous graphene film on SiO2/Si wafers, free from growth-related morphological defects or transfer-induced cracks and folds, remains a formidable challenge. Growth of graphene by chemical vapour deposition on Cu foils has emerged as a powerful technique owing to its compatibility with industrial-scale roll-to-roll technology. However, the polycrystalline nature and microscopic roughness of Cu foils means that such roll-to-roll transferred films are not devoid of cracks and folds. High-fidelity transfer or direct growth of high-quality graphene films on arbitrary substrates is needed to enable wide-ranging applications in photonics or electronics, which include devices such as optoelectronic modulators, transistors, on-chip biosensors and tunnelling barriers. The direct growth of graphene film on an insulating substrate, such as a SiO2/Si wafer, would be useful for this purpose, but current research efforts remain grounded at the proof-of-concept stage, where only discontinuous, nanometre-sized islands can be obtained. Here we develop a face-to-face transfer method for wafer-scale graphene films that is so far the only known way to accomplish both the growth and transfer steps on one wafer. This spontaneous transfer method relies on nascent gas bubbles and capillary bridges between the graphene film and the underlying substrate during etching of the metal catalyst, which is analogous to the method used by tree frogs to remain attached to submerged leaves. In contrast to the previous wet or dry transfer results, the face-to-face transfer does not have to be done by hand and is compatible with any size and shape of substrate; this approach also enjoys the benefit of a much reduced density of transfer defects compared with the conventional transfer method. Most importantly, the direct growth and spontaneous attachment of graphene on the underlying substrate is amenable to batch processing in a semiconductor production line, and thus will speed up the technological application of graphene.

Anomalous Quantum Metal in a 2D Crystalline Superconductor with Electronic Phase Nonuniformity.

The details of the superconducting to quantum metal transition (SQMT) at T = 0 are an open problem that invokes great interest in the nature of this exotic and unexpected ground state (Ephron et al., 1996; Mason and Kapitulnik, 1999; Chervenak and Valles, 2000). However, the SQMT was not yet investigated in a crystalline 2D superconductor with coexisting and fluctuating quantum orders. Here, we report the observation of a SQMT in 2D ion-gel-gated 1T-TiSe2 (Li et al., 2016) driven by a magnetic field. A field-induced crossover between Bose quantum metal and vortex quantum creeping with an increasing field is observed. We discuss the interplay between superconducting and CDW fluctuations (discommensurations) and their relation to the anomalous quantum metal (AQM) phase. From our findings, gate-tunable 1T-TiSe2 emerges as a privileged platform to scrutinize, in a controlled way, the details of the SQMT, the role of coexisting fluctuating orders and, ultimately, to obtain a deeper understanding of the fate of superconductivity in strictly two-dimensional crystals near zero temperature.

Molecular-Beam Epitaxy of Two-Dimensional In2Se3 and Its Giant Electroresistance Switching in Ferroresistive Memory Junction.

Ferroelectric thin film has attracted great interest for nonvolatile memory applications and can be used in either ferroelectric Schottky diodes or ferroelectric tunneling junctions due to its promise of fast switching speed, high on-to-off ratio, and nondestructive readout. Two-dimensional α-phase indium selenide (In2Se3), which has a modest band gap and robust ferroelectric properties stabilized by dipole locking, is an excellent candidate for multidirectional piezoelectric and switchable photodiode applications. However, the large-scale synthesis of this material is still elusive, and its performance as a ferroresistive memory junction is rarely reported. Here, we report the low-temperature molecular-beam epitaxy (MBE) of large-area monolayer α-In2Se3 on graphene and demonstrate the use of α-In2Se3 on graphene in ferroelectric Schottky diode junctions by employing high-work-function gold as the top electrode. The polarization-modulated Schottky barrier formed at the interface exhibits a giant electroresistance ratio of 3.9 × 106 with a readout current density of >12 A/cm2, which is more than 200% higher than the state-of-the-art technology. Our MBE growth method allows a high-quality ultrathin film of In2Se3 to be heteroepitaxially grown on graphene, thereby simplifying the fabrication of high-performance 2D ferroelectric junctions for ferroresistive memory applications.

Quantized Transport, Strain-Induced Perfectly Conducting Modes, and Valley Filtering on Shape-Optimized Graphene Corbino Devices.

The extreme mechanical resilience of graphene and the peculiar coupling it hosts between lattice and electronic degrees of freedom have spawned a strong impetus toward strain-engineered graphene where, on the one hand, strain augments the richness of its phenomenology and makes possible new concepts for electronic devices, and on the other hand, new and extreme physics might take place. Here, we demonstrate that the shape of substrates supporting graphene sheets can be optimized for approachable experiments where strain-induced pseudomagnetic fields (PMF) can be tailored by pressure for directionally selective electronic transmission and pinching-off of current flow down to the quantum channel limit. The Corbino-type layout explored here furthermore allows filtering of charge carriers according to valley and current direction, which can be used to inject or collect valley-polarized currents, thus realizing one of the basic elements required for valleytronics. Our results are based on a framework developed to realistically determine the combination of strain, external parameters, and geometry optimally compatible with the target spatial profile of a desired physical property-the PMF in this case. Characteristic conductance profiles are analyzed through quantum transport calculations on large graphene devices having the optimal shape.

Electron Doping of Ultrathin Black Phosphorus with Cu Adatoms.

Few-layer black phosphorus is a monatomic two-dimensional crystal with a direct band gap that has high carrier mobility for both holes and electrons. Similarly to other layered atomic crystals, like graphene or layered transition metal dichalcogenides, the transport behavior of few-layer black phosphorus is sensitive to surface impurities, adsorbates, and adatoms. Here we study the effect of Cu adatoms onto few-layer black phosphorus by characterizing few-layer black phosphorus field effect devices and by performing first-principles calculations. We find that the addition of Cu adatoms can be used to controllably n-dope few layer black phosphorus, thereby lowering the threshold voltage for n-type conduction without degrading the transport properties. We demonstrate a scalable 2D material-based complementary inverter which utilizes a boron nitride gate dielectric, a graphite gate, and a single bP crystal for both the p- and n-channels. The inverter operates at matched input and output voltages, exhibits a gain of 46, and does not require different contact metals or local electrostatic gating.

Van der Waals force: a dominant factor for reactivity of graphene.

Reactivity control of graphene is an important issue because chemical functionalization can modulate graphene's unique mechanical, optical, and electronic properties. Using systematic optical studies, we demonstrate that van der Waals interaction is the dominant factor for the chemical reactivity of graphene on two-dimensional (2D) heterostructures. A significant enhancement in the chemical stability of graphene is achieved by replacing the common SiO2 substrate with 2D crystals such as an additional graphene layer, WS2, MoS2, or h-BN. Our theoretical and experimental results show that its origin is a strong van der Waals interaction between the graphene layer and the 2D substrate. This results in a high resistive force on graphene toward geometric lattice deformation. We also demonstrate that the chemical reactivity of graphene can be controlled by the relative lattice orientation with respect to the substrates and thus can be used for a wide range of applications including hydrogen storage.

Large Frequency Change with Thickness in Interlayer Breathing Mode--Significant Interlayer Interactions in Few Layer Black Phosphorus.

Bulk black phosphorus (BP) consists of puckered layers of phosphorus atoms. Few-layer BP, obtained from bulk BP by exfoliation, is an emerging candidate as a channel material in post-silicon electronics. A deep understanding of its physical properties and its full range of applications are still being uncovered. In this paper, we present a theoretical and experimental investigation of phonon properties in few-layer BP, focusing on the low-frequency regime corresponding to interlayer vibrational modes. We show that the interlayer breathing mode A(3)g shows a large redshift with increasing thickness; the experimental and theoretical results agree well. This thickness dependence is two times larger than that in the chalcogenide materials, such as few-layer MoS2 and WSe2, because of the significantly larger interlayer force constant and smaller atomic mass in BP. The derived interlayer out-of-plane force constant is about 50% larger than that of graphene and MoS2. We show that this large interlayer force constant arises from the sizable covalent interaction between phosphorus atoms in adjacent layers and that interlayer interactions are not merely of the weak van der Waals type. These significant interlayer interactions are consistent with the known surface reactivity of BP and have been shown to be important for electric-field induced formation of Dirac cones in thin film BP.

Tuning and Persistent Switching of Graphene Plasmons on a Ferroelectric Substrate.

We characterized plasmon propagation in graphene on thin films of the high-κ dielectric PbZr0.3Ti0.7O3 (PZT). Significant modulation (up to ±75%) of the plasmon wavelength was achieved with application of ultrasmall voltages (< ±1 V) across PZT. Analysis of the observed plasmonic fringes at the graphene edge indicates that carriers in graphene on PZT behave as noninteracting Dirac Fermions approximated by a semiclassical Drude response, which may be attributed to strong dielectric screening at the graphene/PZT interface. Additionally, significant plasmon scattering occurs at the grain boundaries of PZT from topographic and/or polarization induced graphene conductivity variation in the interior of graphene, reducing the overall plasmon propagation length. Lastly, through application of 2 V across PZT, we demonstrate the capability to persistently modify the plasmonic response of graphene through transient voltage application.

Hybrid Bilayer WSe2 -CH3 NH3 PbI3 Organolead Halide Perovskite as a High-Performance Photodetector.

A high-performance 2D photodetector based on a bilayer structure comprising a WSe2 monolayer and CH3 NH3 PbI3 organolead halide perovskite is reported. High performance is realized by modification of the WSe2 monolayer with laser healing and perovskite functionalization. After modification, the output of the device was three orders of magnitude better than the pristine device; the performance is superior to that of most of the 2D photodetectors based on transition-metal-dichalcogenides (TMDs). This result indicates that combinatory TMDs-halide perovskite hybrids can be promising building blocks in optoelectronics.

Revealing the atomic site-dependent g factor within a single magnetic molecule via the extended Kondo effect.

The site-dependent g factor of a single magnetic molecule, with intramolecular resolution, is demonstrated for the first time by low-temperature, high-magnetic-field scanning tunneling microscopy of dehydrogenated Mn-phthalocyanine molecules on Au(111). This is achieved by exploring the magnetic-field dependence of the extended Kondo effect at different atomic sites of the molecule. Importantly, an inhomogeneous distribution of the g factor inside a single molecule is revealed. Our results open up a new route to access local spin properties within a single molecule.

Nanometer thick elastic graphene engine.

Significant progress has been made in the construction and theoretical understanding of molecular motors because of their potential use. Here, we have demonstrated fabrication of a simple but powerful 1 nm thick graphene engine. The engine comprises a high elastic membrane-piston made of graphene and weakly chemisorbed ClF3 molecules as the high power volume changeable actuator, while a 532 nm LASER acts as the ignition plug. Rapid volume expansion of the ClF3 molecules leads to graphene blisters. The size of the blister is controllable by changing the ignition parameters. The estimated internal pressure per expansion cycle of the engine is about ∼10(6) Pa. The graphene engine presented here shows exceptional reliability, showing no degradation after 10,000 cycles.

Ultrafast and nanoscale plasmonic phenomena in exfoliated graphene revealed by infrared pump-probe nanoscopy.

Pump-probe spectroscopy is central for exploring ultrafast dynamics of fundamental excitations, collective modes, and energy transfer processes. Typically carried out using conventional diffraction-limited optics, pump-probe experiments inherently average over local chemical, compositional, and electronic inhomogeneities. Here, we circumvent this deficiency and introduce pump-probe infrared spectroscopy with ∼ 20 nm spatial resolution, far below the diffraction limit, which is accomplished using a scattering scanning near-field optical microscope (s-SNOM). This technique allows us to investigate exfoliated graphene single-layers on SiO2 at technologically significant mid-infrared (MIR) frequencies where the local optical conductivity becomes experimentally accessible through the excitation of surface plasmons via the s-SNOM tip. Optical pumping at near-infrared (NIR) frequencies prompts distinct changes in the plasmonic behavior on 200 fs time scales. The origin of the pump-induced, enhanced plasmonic response is identified as an increase in the effective electron temperature up to several thousand Kelvin, as deduced directly from the Drude weight associated with the plasmonic resonances.

Infrared nanoscopy of dirac plasmons at the graphene-SiO2 interface.

We report on infrared (IR) nanoscopy of 2D plasmon excitations of Dirac fermions in graphene. This is achieved by confining mid-IR radiation at the apex of a nanoscale tip: an approach yielding 2 orders of magnitude increase in the value of in-plane component of incident wavevector q compared to free space propagation. At these high wavevectors, the Dirac plasmon is found to dramatically enhance the near-field interaction with mid-IR surface phonons of SiO(2) substrate. Our data augmented by detailed modeling establish graphene as a new medium supporting plasmonic effects that can be controlled by gate voltage.

Biaxial strain in graphene adhered to shallow depressions.

Measurements on graphene exfoliated over a substrate prepatterned with shallow depressions demonstrate that graphene does not remain free-standing but instead adheres to the substrate despite the induced biaxial strain. The strain is homogeneous over the depression bottom as determined by Raman measurements. We find higher Raman shifts and Gruneisen parameters of the phonons underlying the G and 2D bands under biaxial strain than previously reported. Interference modeling is used to determine the vertical position of the graphene and to calculate the optimum dielectric substrate stack for maximum Raman signal.

The Degree of Oxidation of Graphene Oxide.

We show that the degree of oxidation of graphene oxide (GO) can be obtained by using a combination of state-of-the-art ab initio computational modeling and X-ray photoemission spectroscopy (XPS). We show that the shift of the XPS C1s peak relative to pristine graphene, ΔEC1s, can be described with high accuracy by ΔEC1s=A(cO-cl)2+E0, where c0 is the oxygen concentration, A=52.3 eV, cl=0.122, and E0=1.22 eV. Our results demonstrate a precise determination of the oxygen content of GO samples.

Electrically Controlled Thermal Radiation from Reduced Graphene Oxide Membranes.

We demonstrate a fabrication procedure of hybrid devices that consist of reduced graphene oxide films supported by porous polymer membranes that host ionic solutions. We find that we can control the thermal radiation from the surface of reduced graphene oxide through a process of electrically driven reversible ionic intercalation. Through a comparative analysis of the structural, chemical, and optical properties of our reduced graphene oxide films, we identify that the dominant mechanism leading to the intercalation-induced reduction of light emission is Pauli blocking of the interband recombination of charge carriers. We inspect the capabilities of our devices to act as a platform for the electrical control of mid-infrared photonics by observing a bias-induced reduction of apparent temperature of hot surfaces visualized through an infrared thermal camera.

Two-dimensional adaptive membranes with programmable water and ionic channels.

Membranes are ubiquitous in nature with primary functions that include adaptive filtering and selective transport of chemical/molecular species. Being critical to cellular functions, they are also fundamental in many areas of science and technology. Of particular importance are the adaptive and programmable membranes that can change their permeability or selectivity depending on the environment. Here, we explore implementation of such biological functions in artificial membranes and demonstrate two-dimensional self-assembled heterostructures of graphene oxide and polyamine macromolecules, forming a network of ionic channels that exhibit regulated permeability of water and monovalent ions. This permeability can be tuned by a change of pH or the presence of certain ions. Unlike traditional membranes, the regulation mechanism reported here relies on specific interactions between the membranes' internal components and ions. This allows fabrication of membranes with programmable, predetermined permeability and selectivity, governed by the choice of components, their conformation and their charging state.

2D Electrolytes: Theory, Modeling, Synthesis, and Characterization.

A class of compounds sharing the properties of 2D materials and electrolytes, namely 2D electrolytes is described theoretically and demonstrated experimentally. 2D electrolytes dissociate in different solvents, such as water, and become electrically charged. The chemical and physical properties of these compounds can be controlled by external factors, such as pH, temperature, electric permittivity of the medium, and ionic concentration. 2D electrolytes, in analogy with polyelectrolytes, present reversible morphological transitions from 2D to 1D, as a function of pH, due to the interplay of the elastic and Coulomb energies. Since these materials show stimuli-responsive behavior to the environmental conditions, 2D electrolytes can be considered as a novel class of smart materials that expand the functionalities of 2D materials and are promising for applications that require stimuli-responsive demeanor, such as drug delivery, artificial muscles, and energy storage.

Evidence of Spin Frustration in a Vanadium Diselenide Monolayer Magnet.

Monolayer VSe2 , featuring both charge density wave and magnetism phenomena, represents a unique van der Waals magnet in the family of metallic 2D transition-metal dichalcogenides (2D-TMDs). Herein, by means of in situ microscopy and spectroscopic techniques, including scanning tunneling microscopy/spectroscopy, synchrotron X-ray and angle-resolved photoemission, and X-ray absorption, direct spectroscopic signatures are established, that identify the metallic 1T-phase and vanadium 3d1 electronic configuration in monolayer VSe2 grown on graphite by molecular-beam epitaxy. Element-specific X-ray magnetic circular dichroism, complemented with magnetic susceptibility measurements, further reveals monolayer VSe2 as a frustrated magnet, with its spins exhibiting subtle correlations, albeit in the absence of a long-range magnetic order down to 2 K and up to a 7 T magnetic field. This observation is attributed to the relative stability of the ferromagnetic and antiferromagnetic ground states, arising from its atomic-scale structural features, such as rotational disorders and edges. The results of this study extend the current understanding of metallic 2D-TMDs in the search for exotic low-dimensional quantum phenomena, and stimulate further theoretical and experimental studies on van der Waals monolayer magnets.