Publications

The next-nearest-neighbor hopping term ${t}^{\ensuremath{'}}$ determines a magnitude, and, hence, the importance of several phenomena in graphene that include self-doping due to broken bonds and the Klein tunneling, which in the presence of ${t}^{\ensuremath{'}}$, is no longer perfect. Theoretical estimates for ${t}^{\ensuremath{'}}$ vary widely, whereas a few existing measurements by using polarization-resolved magnetospectroscopy have found surprisingly large ${t}^{\ensuremath{'}}$, close to or even exceeding the highest theoretical values. Here, we report dedicated measurements of the density of states in graphene by using high-quality capacitance devices. The density of states exhibits a pronounced electron-hole asymmetry that increases linearly with energy. This behavior yields ${t}^{\ensuremath{'}}$ \ensuremath{\approx} \ensuremath{-}0.3 eV\ifmmode\pm\else\textpm\fi{}15$%$, in agreement with the high end of theory estimates. We discuss the role of electron-electron interactions in determining ${t}^{\ensuremath{'}}$ and overview phenomena, which can be influenced by such a large value of ${t}^{\ensuremath{'}}$.

No abstract is provided for this article.

No abstract is provided for this article.

Interlayer coupling plays a critical role in the electronic band structures and optoelectronic properties of van der Waals (vdW) materials and heterostructures. Here, we utilize optical second-harmonic generation (SHG) measurements to probe the twist-controlled interlayer coupling in artificially stacked WSe2/WSe2 homobilayers and WSe2/WS2 and WSe2/MoS2 heterobilayers with a postannealing procedure. In the large angle twisted WSe2/WSe2 and WSe2/WS2, the angular dependence of the SHG intensity follows the interference relations up to angles above 10°. For lower angles, the SHG is significantly suppressed. Furthermore, for the twisted WSe2/MoS2 the SHG intensity largely deviates from the coherent superposition model and shows consistent quenching for all the stacking angles. The suppressed SHG in twisted transition metal dichalcogenide (TMDC) bilayers is predominantly attributed to the interlayer coupling between the two adjacent monolayers. The evolution of the interlayer Raman mode in WSe2 demonstrates that the interlayer coupling in the twisted WSe2/WSe2 and WSe2/WS2 is highly angle-dependent. Alternatively, the interlayer coupling generally exists in the twisted WSe2/MoS2, regardless of the different angles. The interlayer coupling is further confirmed by the quenching and red-shift of the photoluminescence of WSe2 in the twisted TMDC bilayers. Combined with density functional theory calculations, we reveal that the stacking-angle-modulated interlayer coupling originates from the variation of the interlayer spacing and the binding energy in the twisted TMDC bilayers.

The impulsive optical excitation of carriers in graphene creates an out-of-equilibrium distribution, which thermalizes on an ultrafast timescale [1-4]. This hot Fermi-Dirac (FD) distribution subsequently cools via phonon emission within few hundreds of femtoseconds. While the relaxation mechanisms mediated by phonons have been extensively investigated, the initial stages, ruled by fundamental electron-electron (e-e) interactions still pose a challenge.

Thermally activated ultrafast diffusion, collision and combination of metal atoms comprise the fundamental processes of synthesizing burgeoning subnanometer metal clusters for diverse applications. However, so far, no method has allowed the kinetically controllable synthesis of subnanometer metal clusters without compromising metal loading. Herein, we have developed, for the first time, a graphene-confined ultrafast radiant heating (GCURH) method for the synthesis of high-loading metal cluster catalysts in microseconds, where the impermeable and flexible graphene acts as a diffusion-constrained nanoreactor for high-temperature reactions. Originating from graphene-mediated ultrafast and efficient laser-to-thermal conversion, the GCURH method is capable of providing a record-high heating and cooling rate of ∼109°C/s and a peak temperature above 2000°C, and the diffusion of thermally activated atoms is spatially limited within the confinement of the graphene nanoreactor. As a result, due to the kinetics-dominant and diffusion-constrained condition provided by GCURH, subnanometer Co cluster catalysts with high metal loading up to 27.1 wt% have been synthesized by pyrolyzing a Co-based metal-organic framework (MOF) in microseconds, representing one of the highest size-loading combinations and the quickest rate for MOF pyrolysis in the reported literature. The obtained Co cluster catalyst not only exhibits an extraordinary activity similar to that of most modern multicomponent noble metal counterparts in the electrocatalytic oxygen evolution reaction, but is also highly convenient for catalyst recycling and refining due to its single metal component. Such a novel GCURH technique paves the way for the kinetically regulated, limited diffusion distance of thermally activated atoms, which in turn provides enormous opportunities for the development of sophisticated and environmentally sustainable metal cluster catalysts.

The recent advent of atomically-thin ferromagnetic crystals has allowed experimental studies of two-dimensional (2D) magnetism that not only exhibits novel behavior due to the reduced dimensionality but also often serves as a starting point for understanding of the magnetic properties of bulk materials. Here we employ ballistic Hall micromagnetometry to study magnetization of individual 2D ferromagnets. Our devices are multilayer van der Waals (vdW) heterostructures comprising of an atomically-thin ferromagnetic crystal placed on top of a Hall bar made from encapsulated graphene. 2D ferromagnets can be replaced repeatedly, making the graphene-based Hall magnetometers reusable and expanding a range of their possible applications. The technique is applied for the quantitative analysis of magnetization and its behavior in atomically thin CrBr3. The compound is found to remain ferromagnetic down to a monolayer thickness and exhibit high out-of-plane anisotropy. We report how the critical temperature changes with the number of layers and how domain walls propagate through the ultimately thin ferromagnets. The temperature dependence of magnetization varies little with thickness, in agreement with the strongly layered nature of CrBr3. The observed behavior is markedly different from that given by the simple 2D Ising model normally expected to describe 2D easy-axis ferromagnetism. Due to the increasingly common usage of vdW assembly, the reported approach offers vast possibilities for investigation of 2D magnetism and related phenomena.

One of the fundamental properties of spin 1/2 particles is their interaction with magnetic fields. The exploration of this coupling can be quite elusive, for example in the case of neutrinos. Graphene has been shown to be a condensed matter platform for the study of such ultrarelativistic particles, with its neutrino-like charge carriers having a spin-like degree of freedom called pseudospin. Here we show that in analogy to the spin alignment of a fermion in a magnetic field, the pseudo-spin of graphene can be oriented by a strain induced pseudo-magnetic field through the Zeeman term. We reveal this pseudo-spin polarization as a sublattice symmetry breaking by tunably straining graphene using the tip of a scanning tunnelling microscope. The observed pseudo-spin polarization scales with the lifting height of the strained deformation and therefore with the pseudo-magnetic field strength. Its magnitude is quantitatively reproduced by analytic and tight-binding models. This adds a key ingredient to the celebrated analogy of graphene's charge carriers to ultra-relativistic Dirac fermions. Furthermore, the deduced fields of about 1000 T could provide an effective THz valley filter, as a basic element of valleytronics.

Water molecules at the solid-liquid interface display intricate behaviours sensitive to small changes. The presence of different interfacial components, such as cations or functional groups, shape the physical and chemical properties of the hydrogen bond network. Understanding such interfacial hydrogen-bond networks is essential for a large range of applications and scientific questions. To probe the interfacial hydrogen-bond network, atmospheric water capture is a powerful tool. Here, we experimentally observe that a calcium ion on a calcium-intercalated graphene oxide aerogel (Ca-GOA) surface captures 3.2 times more water molecules than in its freestanding state. From experimental Van’t Hoff estimation and density functional theory (DFT) calculations, we uncover the synergistically enhanced hydrogen-bond network of the calcium ion-epoxide complex due to significantly larger polarizations and hydrogen bond enthalpies. This study reveals valuable insights into the interfacial water hydrogen-bond network on functionalized carbon-cation complexed surfaces and potential pathways for future atmospheric water generation technologies.

Defect centers in insulators play a critical role in creating important functionalities in materials: prototype qubits, single-photon sources, magnetic field probes, and pressure sensors. These functionalities are highly dependent on their midgap electronic structure and orbital/spin wave function contributions. However, in most cases, these fundamental properties remain unknown or speculative due to the defects being deeply embedded beneath the surface of highly resistive host crystals, thus impeding access through surface probes. Here, we directly inspected the atomic and electronic structures of defects in thin carbon-doped hexagonal boron nitride (hBN:C) by using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). Such investigation adds direct information about the electronic midgap states to the well-established photoluminescence response (including single-photon emission) of intentionally created carbon defects in the most commonly investigated van der Waals insulator. Our joint atomic-scale experimental and theoretical investigations reveal two main categories of defects: (1) single-site defects manifesting as donor-like states with atomically resolved structures observable via STM and (2) multisite defect complexes exhibiting a ladder of empty and occupied midgap states characterized by distinct spatial geometries. Combining direct probing of midgap states through tunneling spectroscopy with the inspection of the optical response of insulators hosting specific defect structures holds promise for creating and enhancing functionalities realized with individual defects in the quantum limit. These findings underscore not only the versatility of hBN:C as a platform for quantum defect engineering but also its potential to drive advancements in atomic-scale optoelectronics.

When two-dimensional atomic crystals are brought into close proximity to form a van der Waals heterostructure, neighbouring crystals can start influencing each others electronic properties. Of particular interest is the situation when the periodicity of the two crystals closely match and a moir\'e pattern forms, which results in specific electron scattering, reconstruction of electronic and excitonic spectra, crystal reconstruction, and many other effects. Thus, formation of moir\'e patterns is a viable tool of controlling the electronic properties of 2D materials. At the same time, the difference in the interatomic distances for the two crystals combined, determines the range in which the electronic spectrum is reconstructed, and thus is a barrier to the low energy regime. Here we present a way which allows spectrum reconstruction at all energies. By using graphene which is aligned simultaneously to two hexagonal boron nitride layers, one can make electrons scatter in the differential moir\'e pattern, which can have arbitrarily small wavevector and, thus results in spectrum reconstruction at arbitrarily low energies. We demonstrate that the strength of such a potential relies crucially on the atomic reconstruction of graphene within the differential moir\'e super-cell. Such structures offer further opportunity in tuning the electronic spectra of two-dimensional materials.

No abstract is provided for this article.

Marcus-Hush theory of electron transfer is one of the pillars of modern electrochemistry with a large body of supporting experimental evidence presented to date. However, some predictions, such as the electrochemical behavior at disk ultramicroelectrodes, remain unverified. Herein, we present a study of electron tunneling across a hexagonal boron nitride acting as a barrier between a graphite electrode and redox mediators in a liquid solution. This was achieved by the fabrication of disk ultramicroelectrodes with a typical diameter of 5 μm. Analysis of voltammetric measurements, using two common outer-sphere redox mediators, yielded several electrochemical parameters, including the electron transfer rate constant, limiting current, and transfer coefficient. They depart significantly from the Butler-Volmer kinetics and instead show behavior previously predicted by the Marcus-Hush theory of electron transfer. In addition, our system provides a noteworthy experimental platform, which could be applied to address a number of scientific problems such as identification of reaction mechanisms, surface modification, or long-range electron transfer.

Graphene oxide (GO) based multi-layered membranes have shown outstanding molecular-sieving properties for gas separation, surpassing the upper bound for polymeric membranes especially for hydrogen decarbonization. At the same time, the mechanism of gas permeation through such 2D GO membranes is very different in comparison to the traditional polymeric membranes due to multilayer, laminated nature of the former. For strategical design of novel membranes based on two-dimensional materials, it is important to understand the mechanism and to be able to measure two key parameters for gas transport: solubility and diffusivity. Such measurements are well established for the characterization of transport properties of bulk polymeric membranes. However, it is still a challenge to measure gas diffusion coefficients directly and accurately in ultra-thin multi-layered membranes. The lack of characterization limits our understanding of the mechanisms of gas transport though such membranes. In this work, we applied a time lag method to determine the diffusivities for He, H2, O2, N2, CH4, CO2 and equimolar mixture by on-line mass spectrometry. In contrast to polymeric membranes, the diffusivity and diffusion activation energy for all gases in 2D membranes are exponentially dependent on membrane thickness. Thus, in 2D membrane we can use an easy strategy to precisely regulate permeability and selectivity by the adjustment of the number of nanolayers, which is not possible using traditional polymeric membranes. This study is important for both the characterization and the standardization of gas transport properties of multi-layered membranes, and the design of novel membranes based on 2D materials.