Spontaneous Time-Reversal Symmetry Breaking at Individual Grain Boundaries in Graphene.

Graphene grain boundaries (GBs) have attracted interest for their ability to host nearly dispersionless electronic bands and magnetic instabilities. Here, we employ quantum transport and universal conductance fluctuation measurements to experimentally demonstrate a spontaneous breaking of time-reversal symmetry across individual GBs of chemical vapor deposited graphene. While quantum transport across the GBs indicate spin-scattering-induced dephasing and hence formation of local magnetic moments, below T≲4 K we observe complete lifting of time-reversal symmetry at high carrier densities (n≳5×10^{12} cm^{-2}) and low temperature (T≲2 K). An unprecedented thirtyfold reduction in the universal conductance fluctuation magnitude with increasing doping density further supports the possibility of an emergent frozen magnetic state at the GBs. Our experimental results suggest that realistic GBs of graphene can be a promising resource for new electronic phases and spin-based applications.

Optical Control of Non-Equilibrium Phonon Dynamics.

The light-induced selective population of short-lived far-from-equilibrium vibration modes is a promising approach for controlling ultrafast and irreversible structural changes in functional nanomaterials. However, this requires a detailed understanding of the dynamics and evolution of these phonon modes and their coupling to the excited-state electronic structure. Here, we combine femtosecond mega-electronvolt electron diffraction experiments on a prototypical layered material, MoTe2, with non-adiabatic quantum molecular dynamics simulations and ab initio electronic structure calculations to show how non-radiative energy relaxation pathways for excited electrons can be tuned by controlling the optical excitation energy. We show how the dominant intravalley and intervalley scattering mechanisms for hot and band-edge electrons leads to markedly different transient phonon populations evident in electron diffraction patterns. This understanding of how tuning optical excitations affect phonon populations and atomic motion is critical for efficiently controlling light-induced structural transitions of optoelectronic devices.

Effect of Carrier Localization on Electrical Transport and Noise at Individual Grain Boundaries in Monolayer MoS2.

Despite its importance in the large-scale synthesis of transition metal dichalcogenides (TMDC) molecular layers, the generic quantum effects on electrical transport across individual grain boundaries (GBs) in TMDC monolayers remain unclear. Here we demonstrate that strong carrier localization due to the increased density of defects determines both temperature dependence of electrical transport and low-frequency noise at the GBs of chemical vapor deposition (CVD)-grown MoS2 layers. Using field effect devices designed to explore transport across individual GBs, we show that the localization length of electrons in the GB region is ∼30-70% lower than that within the grain, even though the room temperature conductance across the GB, oriented perpendicular to the overall flow of current, may be lower or higher than the intragrain region. Remarkably, we find that the stronger localization is accompanied by nearly 5 orders of magnitude enhancement in the low-frequency noise at the GB region, which increases exponentially when the temperature is reduced. The microscopic framework of electrical transport and noise developed in this paper may be readily extended to other strongly localized two-dimensional systems, including other members of the TMDC family.

Magnitude and Origin of Electrical Noise at Individual Grain Boundaries in Graphene.

Grain boundaries (GBs) are undesired in large area layered 2D materials as they degrade the device quality and their electronic performance. Here we show that the grain boundaries in graphene which induce additional scattering of carriers in the conduction channel also act as an additional and strong source of electrical noise especially at the room temperature. From graphene field effect transistors consisting of single GB, we find that the electrical noise across the graphene GBs can be nearly 10 000 times larger than the noise from equivalent dimensions in single crystalline graphene. At high carrier densities (n), the noise magnitude across the GBs decreases as ∝1/n, suggesting Hooge-type mobility fluctuations, whereas at low n close to the Dirac point, the noise magnitude could be quantitatively described by the fluctuations in the number of propagating modes across the GB.

Fermi-edge transmission resonance in graphene driven by a single Coulomb impurity.

The interaction between the Fermi sea of conduction electrons and a nonadiabatic attractive impurity potential can lead to a power-law divergence in the tunneling probability of charge through the impurity. The resulting effect, known as the Fermi edge singularity (FES), constitutes one of the most fundamental many-body phenomena in quantum solid state physics. Here we report the first observation of FES for Dirac fermions in graphene driven by isolated Coulomb impurities in the conduction channel. In high-mobility graphene devices on hexagonal boron nitride substrates, the FES manifests in abrupt changes in conductance with a large magnitude ≈e(2)/h at resonance, indicating total many-body screening of a local Coulomb impurity with fluctuating charge occupancy. Furthermore, we exploit the extreme sensitivity of graphene to individual Coulomb impurities and demonstrate a new defect-spectroscopy tool to investigate strongly correlated phases in graphene in the quantum Hall regime.

Probing Interlayer Interactions and Commensurate-Incommensurate Transition in Twisted Bilayer Graphene through Raman Spectroscopy.

Twisted 2D layered materials have garnered much attention recently as a class of 2D materials whose interlayer interactions and electronic properties are dictated by the relative rotation/twist angle between the adjacent layers. In this work, we explore a prototype of such a twisted 2D system, artificially stacked twisted bilayer graphene (TBLG), where we probe, using Raman spectroscopy, the changes in the interlayer interactions and electron-phonon scattering pathways as the twist angle is varied from 0° to 30°. The long-range Moiré potential of the superlattice gives rise to additional intravalley and intervalley scattering of the electrons in TBLG, which has been investigated through their Raman signatures. Density functional theory (DFT) calculations of the electronic band structure of the TBLG superlattices were found to be in agreement with the resonant Raman excitations across the van Hove singularities in the valence and conduction bands predicted for TBLG due to hybridization of bands from the two layers. We also observe that the relative rotation between the graphene layers has a marked influence on the second order overtone and combination Raman modes signaling a commensurate-incommensurate transition in TBLG as the twist angle increases. This serves as a convenient and rapid characterization tool to determine the degree of commensurability in TBLG systems.

Direct observation of valley hybridization and universal symmetry of graphene with mesoscopic conductance fluctuations.

In graphene, the valleys represent spinlike quantities and can act as a physical resource in valley-based electronics to produce novel quantum computation schemes. Here we demonstrate a direct route to tune and read the valley quantum states of disordered graphene by measuring the mesoscopic conductance fluctuations. We show that the conductance fluctuations in graphene at low temperatures are reduced by a factor of 4 when valley triplet states are gapped in the presence of short-range potential scatterers at high carrier densities. We also show that this implies a gate tunable universal symmetry class that outlines a fundamental feature arising from graphene's unique crystal structure.

Review of strategies toward the development of alloy two-dimensional (2D) transition metal dichalcogenides.

Atomically thin two-dimensional (2D) transition metal dichalcogenides (TMDCs) have attracted significant attention owing to their prosperity in material research. The inimitable features of TMDCs triggered the emerging applications in diverse areas. In this review, we focus on the tailored and engineering of the crystal lattice of TMDCs that finally enhance the efficiency of the material properties. We highlight several preparation techniques and recent advancements in compositional engineering of TMDCs structure. We summarize different approaches for TMDCs such as doping and alloying with different materials, alloying with other 2D metals, and scrutinize the technological potential of these methods. Beyond that, we also highlight the recent significant advancement in preparing 2D quasicrystals and alloying the 2D TMDCs with MAX phases. Finally, we highlight the future perspectives for crystal engineering in TMDC materials for structure stability, machine learning concept marge with materials, and their emerging applications.

Atomically thin gallium layers from solid-melt exfoliation.

Among the large number of promising two-dimensional (2D) atomic layer crystals, true metallic layers are rare. Using combined theoretical and experimental approaches, we report on the stability and successful exfoliation of atomically thin "gallenene" sheets on a silicon substrate, which has two distinct atomic arrangements along crystallographic twin directions of the parent α-gallium. With a weak interface between solid and molten phases of gallium, a solid-melt interface exfoliation technique is developed to extract these layers. Phonon dispersion calculations show that gallenene can be stabilized with bulk gallium lattice parameters. The electronic band structure of gallenene shows a combination of partially filled Dirac cone and the nonlinear dispersive band near the Fermi level, suggesting that gallenene should behave as a metallic layer. Furthermore, it is observed that the strong interaction of gallenene with other 2D semiconductors induces semiconducting to metallic phase transitions in the latter, paving the way for using gallenene as promising metallic contacts in 2D devices.

Structural Phase Transformation in Strained Monolayer MoWSe2 Alloy.

Two-dimensional (2D) materials exhibit different mechanical properties from their bulk counterparts owing to their monolayer atomic thickness. Here, we have examined the mechanical behavior of 2D molybdenum tungsten diselenide (MoWSe2) precipitation alloy grown using chemical vapor deposition and composed of numerous nanoscopic MoSe2 and WSe2 regions. Applying a bending strain blue-shifted the MoSe2 and WSe2 A1g Raman modes with the stress concentrated near the precipitate interfaces predominantly affecting the WSe2 modes. In situ local Raman measurements suggested that the crack propagated primarily thorough MoSe2-rich regions in the monolayer alloy. Molecular dynamics (MD) simulations were performed to study crack propagation in an MoSe2 monolayer containing nanoscopic WSe2 regions akin to the experiment. Raman spectra calculated from MD trajectories of crack propagation confirmed the emergence of intermediate peaks in the strained monolayer alloy, mirroring experimental results. The simulations revealed that the stress buildup around the crack tip caused an irreversible structural transformation from the 2H to 1T phase both in the MoSe2 matrix and WSe2 patches. This was corroborated by high-angle annular dark-field images. Crack branching and subsequent healing of a crack branch were also observed in WSe2, indicating the increased toughness and crack propagation resistance of the alloyed 2D MoWSe2 over the unalloyed counterparts.

Exfoliation of a non-van der Waals material from iron ore hematite.

With the advent of graphene, the most studied of all two-dimensional materials, many inorganic analogues have been synthesized and are being exploited for novel applications. Several approaches have been used to obtain large-grain, high-quality materials. Naturally occurring ores, for example, are the best precursors for obtaining highly ordered and large-grain atomic layers by exfoliation. Here, we demonstrate a new two-dimensional material 'hematene' obtained from natural iron ore hematite (α-Fe2O3), which is isolated by means of liquid exfoliation. The two-dimensional morphology of hematene is confirmed by transmission electron microscopy. Magnetic measurements together with density functional theory calculations confirm the ferromagnetic order in hematene while its parent form exhibits antiferromagnetic order. When loaded on titania nanotube arrays, hematene exhibits enhanced visible light photocatalytic activity. Our study indicates that photogenerated electrons can be transferred from hematene to titania despite a band alignment unfavourable for charge transfer.

Quaternary 2D Transition Metal Dichalcogenides (TMDs) with Tunable Bandgap.

Alloying/doping in 2D material is important due to wide range bandgap tunability. Increasing the number of components would increase the degree of freedom which can provide more flexibility in tuning the bandgap and also reduces the growth temperature. Here, synthesis of quaternary alloys Mox W1-x S2y Se2(1-y) is reported using chemical vapor deposition. The composition of alloys is tuned by changing the growth temperatures. As a result, the bandgap can be tuned which varies from 1.61 to 1.85 eV. The detailed theoretical calculation supports the experimental observation and shows a possibility of wide tunability of bandgap.

Re Doping in 2D Transition Metal Dichalcogenides as a New Route to Tailor Structural Phases and Induced Magnetism.

Alloying in 2D results in the development of new, diverse, and versatile systems with prospects in bandgap engineering, catalysis, and energy storage. Tailoring structural phase transitions using alloying is a novel idea with implications in designing all 2D device architecture as the structural phases in 2D materials such as transition metal dichalcogenides are correlated with electronic phases. Here, this study develops a new growth strategy employing chemical vapor deposition to grow monolayer 2D alloys of Re-doped MoSe2 with show composition tunable structural phase variations. The compositions where the phase transition is observed agree well with the theoretical predictions for these 2D systems. It is also shown that in addition to the predicted new electronic phases, these systems also provide opportunities to study novel phenomena such as magnetism which broadens the range of their applications.

Metal Immiscibility Route to Synthesis of Ultrathin Carbides, Borides, and Nitrides.

Ultrathin ceramic coatings are of high interest as protective coatings from aviation to biomedical applications. Here, a generic approach of making scalable ultrathin transition metal-carbide/boride/nitride using immiscibility of two metals is demonstrated. Ultrathin tantalum carbide, nitride, and boride are grown using chemical vapor deposition by heating a tantalum-copper bilayer with corresponding precursor (C2 H2 , B powder, and NH3 ). The ultrathin crystals are found on the copper surface (opposite of the metal-metal junction). A detailed microscopy analysis followed by density functional theory based calculation demonstrates the migration mechanism, where Ta atoms prefer to stay in clusters in the Cu matrix. These ultrathin materials have good interface attachment with Cu, improving the scratch resistance and oxidation resistance of Cu. This metal-metal immiscibility system can be extended to other metals to synthesize metal carbide, boride, and nitride coatings.

Fluorinated h-BN as a magnetic semiconductor.

We report the fluorination of electrically insulating hexagonal boron nitride (h-BN) and the subsequent modification of its electronic band structure to a wide bandgap semiconductor via introduction of defect levels. The electrophilic nature of fluorine causes changes in the charge distribution around neighboring nitrogen atoms in h-BN, leading to room temperature weak ferromagnetism. The observations are further supported by theoretical calculations considering various possible configurations of fluorinated h-BN structure and their energy states. This unconventional magnetic semiconductor material could spur studies of stable two-dimensional magnetic semiconductors. Although the high thermal and chemical stability of h-BN have found a variety of uses, this chemical functionalization approach expands its functionality to electronic and magnetic devices.

Ultrafast non-radiative dynamics of atomically thin MoSe2.

Photo-induced non-radiative energy dissipation is a potential pathway to induce structural-phase transitions in two-dimensional materials. For advancing this field, a quantitative understanding of real-time atomic motion and lattice temperature is required. However, this understanding has been incomplete due to a lack of suitable experimental techniques. Here, we use ultrafast electron diffraction to directly probe the subpicosecond conversion of photoenergy to lattice vibrations in a model bilayered semiconductor, molybdenum diselenide. We find that when creating a high charge carrier density, the energy is efficiently transferred to the lattice within one picosecond. First-principles nonadiabatic quantum molecular dynamics simulations reproduce the observed ultrafast increase in lattice temperature and the corresponding conversion of photoenergy to lattice vibrations. Nonadiabatic quantum simulations further suggest that a softening of vibrational modes in the excited state is involved in efficient and rapid energy transfer between the electronic system and the lattice.

Microscopic mechanism of 1/f noise in graphene: role of energy band dispersion.

A distinctive feature of single-layer graphene is the linearly dispersive energy bands, which in the case of multilayer graphene become parabolic. A simple electrical transport-based probe to differentiate between these two band structures will be immensely valuable, particularly when quantum Hall measurements are difficult, such as in chemically synthesized graphene nanoribbons. Here we show that the flicker noise, or the 1/f noise, in electrical resistance is a sensitive and robust probe to the band structure of graphene. At low temperatures, the dependence of noise magnitude on the carrier density was found to be opposite for the linear and parabolic bands. We explain our data with a comprehensive theoretical model that clarifies several puzzling issues concerning the microscopic origin of flicker noise in graphene field-effect transistors (GraFET).