2D Atomic Crystal Research Articles

Excitons at the interface of 2D TMDs and molecular semiconductors.

Van der Waals heterostructures (vdWHs) of vertically stacked two-dimensional (2D) atomic crystals have been used to elicit intriguing phenomena stemming from strong electronic correlations, magnetic textures, and interlayer excitons spawned at the heterointerface. However, vdWHs comprised of heterointerfaces between these 2D atomic crystal lattices and molecular assemblies are emerging as equally intriguing platforms supporting properties to be harnessed for photovoltaic energy conversion, photodetection, spin-selective charge injection, and quantum emission. In this perspective, we summarize recent research examining exciton dynamics in heterostructures between semiconducting 2D transition metal dichalcogenides and molecular organic semiconductors. We discuss methods for assembly of these heterostructures, the nature of interlayer or charge-transfer excitons at transition-metal dichalcogenide (TMD)-molecule interfaces, explicit exciton transfer between organics and TMDs, and other interfacial phenomena driven by the merger of these two material classes. We also suggest key new research directions extending the remit of these 2D atomic-molecular lattice heterointerfaces into the domains of condensed matter physics, quantum sensing, and energy conversion.

Advanced electrochemical energy storage and conversion on graphdiyne interface

The research in graphdiyne (GDY) has experienced a rapid growth period in the first decade after its birth. As a new two-dimensional (2D) atomic crystal, GDY has unique structures consisting of both sp and sp² hybridized carbon atoms, and exhibits many unprecedented intrinsic properties to scientists. Due to the inherent characteristics of GDY, some new phenomena and properties have been discovered in a wide range of research fields. GDY has made substantial breakthroughs in fundamental and applied science, formed innovative scientific concepts, and made great achievements. In these fields, the electrochemical energy storage and conversion are two important and impressive fields for the fundamental applicative investigations. This review focuses on the utilization of GDY as advanced electrochemical interface for the electrochemical energy storage and conversion. It begins with an introduction of the superiorities and inherent compatibilities of GDY as the electrochemical interface. Then, GDY's recent achievements in electrochemical storage and conversion are commented, from which we can appreciate the inherent advantages of GDY as a crucial material for alternating and innovating the electrochemical interface. Finally, new insights into the challenges and further perspectives on the GDY interface for the electrochemical energy storage and conversion are discussed, aiming at prompting in-depth investigation and their performance in practical applications.

Ultrathin Hafnium Disulfide Atomic Crystals with ROS-Scavenging and Colon-Targeting Capabilities for Inflammatory Bowel Disease Treatment.

The exciting success of NBTXR3 in the clinic has triggered a tumult of activities in the design and development of hafnium-based nanoparticles. However, due to the concerns of nondegradation and limited functions, the biomedical applications of Hf-based nanoparticles mainly focus on tumors. Herein, tannic acid capped hafnium disulfide (HfS2@TA) nanosheets, a 2D atomic crystal of hafnium-based materials prepared by liquid-phase exfoliation, were explored as high-performance anti-inflammatory nanoagents for the targeted therapy of inflammatory bowel disease (IBD). Benefiting from the transformation of the S2-/S6+ valence state and huge specific surface area, the obtained HfS2@TA nanosheets were not only capable of effectively eliminating reactive oxygen species/reactive nitrogen species and downregulating pro-inflammatory factors but also could be excreted via kidney and hepatointestinal systems. Unexpectedly, HfS2@TA maintained excellent targeting capability to an inflamed colon even in the harsh digestive tract environment, mainly attributed to the electrostatic interactions between negatively charged tannic acid and positively charged inflamed epithelium. Encouragingly, upon oral or intravenous administration, HfS2@TA quickly inhibited inflammation and repaired the intestinal mucosa barrier in both dextran sodium sulfate and 2,4,6-trinitrobenzenesulfonic acid induced IBD models. This work demonstrated that ultrathin HfS2@TA atomic crystals with enhanced colon accumulation were promising for the targeted therapy of IBD.

Using in-plane anisotropy to engineer Janus monolayers of rhenium dichalcogenides

The new class of Janus two-dimensional (2D) transition-metal dichalcogenides with two different interfaces are currently gaining increasing attention due to their distinct properties different from the typical 2D materials. Here, we show that in-plane anisotropy of a 2D atomic crystal, like ReS$_{2}$ or ReSe$_{2}$, allows formation of a large number of inequivalent Janus monolayers. We use first-principles calculations to investigate the structural stability of 29 distinct ReX$_{2-x}$Y$_{x}$ ($\mathrm{X,Y \in \{S,Se\}}$) structures, which can be obtained by selective exchange of exposed chalcogens in a ReX$_{2}$ monolayer. We also examine the electronic properties and work function of the most stable Janus monolayers and show that the large number of inequivalent structures provides a way to engineer spin-orbit splitting of the electronic bands. We find that the breaking of inversion symmetry leads to sizable spin splittings and spontaneous diople moments than are larger than those in other Janus dichalcogenides. Moreover, our caluclations suggest that the work function of the Janus monolayers can be tuned by varying the content of the substituting chalcogen. Our work demonstrates that in-plane anisotropy provides additional flexibility in sub-layer engineering of 2D atomic crystals.

Single-Atom Tailoring of Two-Dimensional Atomic Crystals Enables Highly Efficient Detection and Pattern Recognition of Chemical Vapors

Low-dimensional semiconductor materials, such as single-walled carbon nanotubes, two-dimensional (2D) atomic crystals, and organic frameworks, have been widely adapted as ideal platforms to construct various chemo/biosensors with satisfying sensitivity. However, the general drawbacks in chemiresistive devices, including high operation temperatures, low response to low-polarity molecules, and poor selectivity, have limited their real-world applications. In this study, 2D materials (graphene, MoS2, and WSe2) were systematically functionalized with series of monodispersed single atomic sites (Pt, Co, and Ru) through a facile approach to construct single-atom sensors (SASs) for the detection of VOCs at room temperature. The structural and catalytic characteristics of SAs successfully translated into enhanced gas-sensing performance, with a 1-2 orders of magnitude increase in relative response to ethanol (@5 ppm) and acetone (@20 ppm) vapors (in all M-2D SASs as compared to pristine substrates), high selectivity to VOCs against relative humidity (M-WSe2 SASs), and fast response/recovery time (11/58 s for Pt-Graphene and 22/48 s for Pt-MoS2 to 50 ppm ethanol, 9/57 s for Pt-Graphene and 15/75 s for Pt-MoS2 to 200 ppm acetone) that are several times faster than the pristine 2D materials. Density functional theory (DFT) calculations revealed the signaling mechanism in SASs, and the data were further trained to build machine learning (ML) models for predicting the adsorption energies and sensing performance using the features of adsorption heights, metal charge, and charge transfer between the adsorbed VOCs and SASs sites. Finally, the rich combination of the metal single atoms and 2D atomic crystal supports were converted to cross-sensitive SA sensor array that allows for detection and identification of different VOCs.

Intercalation and hybrid heterostructure integration of two-dimensional atomic crystals with functional organic semiconductor molecules

Van der Waals (vdW) integration affords semiconductor heterostructures without constrains of lattice matching and opens up a new realm of functional devices by design. A particularly interesting approach is the electrochemical intercalation of two-dimensional (2D) atomic crystal and formation of superlattices, which can provide scalable production of novel vdW heterostructures. However, this approach has been limited to the use of organic cations with non-functional aliphatic chains, therefore failed to take the advantage of the vast potentials in molecular functionalities (electronic, photonic, magnetic, etc.). Here we report the integration of 2D crystal (MoS2, WS2, highly oriented pyrolytic graphite (HOPG), WSe2 as model systems) with electrochemically inert organic molecules that possess semiconducting characteristics (including perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA), pentacene and fullerene), through on-chip electrochemical intercalation. An unprecedented long-range spatial feature of intercalation has been achieved, which allowed facile assembly of a vertical MoS2-PTCDA-Si junction. The intercalated heterostructure shows significant modulation of the lateral transport, and leads to a molecular tunneling characteristic at the vertical direction. The general intercalation of charge neutral and functional molecules defines a versatile platform of inorganic/organic hybrid vdW heterostructures with significantly extended molecular functional building blocks, holding great promise in future design of nano/quantum devices.

Evidence for Helical Hinge Zero Modes in an Fe-Based Superconductor.

Combining topology and superconductivity provides a powerful tool for investigating fundamental physics as well as a route to fault-tolerant quantum computing. There is mounting evidence that the Fe-based superconductor FeTe0.55Se0.45 (FTS) may also be topologically nontrivial. Should the superconducting order be s±, then FTS could be a higher order topological superconductor with helical hinge zero modes (HHZMs). To test the presence of these modes, we have fabricated normal-metal/superconductor junctions on different surfaces via 2D atomic crystal heterostructures. As expected, junctions in contact with the hinge reveal a sharp zero bias anomaly that is absent when tunneling purely into the c-axis. Additionally, the shape and suppression with temperature are consistent with highly coherent modes along the hinge and are incongruous with other origins of zero bias anomalies. Additional measurements with soft-point contacts in bulk samples with various Fe interstitial contents demonstrate the intrinsic nature of the observed mode. Thus, we provide evidence that FTS is indeed a higher order topological superconductor.

Electric switching of magnetism in 2D.

Combined electrostatic gating and magnetic fields switch a 2D atomic crystal from an antiferromagnetic to a ferromagnetic state.

Recent advance in two-dimensional group-IV metal chalcogenides

As complementary materials to zero-band-gap graphene, two-dimensional (2D) transition metal dichalcogenides (TMDCs) with sizable band gaps have attracted much attention. However, 2D group-IV metal chalcogenides such as SnSe and GeS have rarely been studied. Group-IV metal chalcogenides have been studied for a long time in the field of solar cell and photoelectric converter owing to their appropriate bandgaps. Recently, the highest ZT value of thermoelectric was discovered in the bulk SnSe crystal. It has been reported that layered group-IV metal chalcogenides are phase change materials, which endows them enriched properties. Theoretical calculations predict that 2D group-IV metal chalcogenides have excellent thermoelectricity, ferroelectricity and piezoelectricity and thus are promising building blocks for functional devices. However, these intriguing properties of 2D group-IV metal chalcogenides have scarcely been detected from experimental aspects. A number of reviews on 2D atomic crystals have included a brief introduction of group-IV metal chalcogenides, but a specific review on the recent advance in 2D group-IV metal chalcogenides is necessary to provide in-depth insights to this emerging family of 2D materials. In this review, we first summarized the crystallographic structures and band-gaps of 2D group-IV metal chalcogenides, revealed the dependence of band-gaps with number of layers and also correlated the properties with the structures of these 2D group-IV metal chalcogenides. We then discussed the progress in the synthesis of these materials and concluded that the lacking of controllable synthesis methods greatly hindered the studies on these materials. We also summarized the properties of these 2D materials from both theoretical calculations and experimental aspects. When the thickness of these materials is reduced to monolayer, they exhibit outstanding thermoelectricity, ferroelectricity and piezoelectricity compared with other 2D atomic crystal such as the most widely studied graphene and MoS2. The similar structures between 2D group-IV metal chalcogenides and black phosphorus provide them with anisotropic optical properties. However, their superior stability under ambient condition makes them promising candidates for practical devices. Finally, we summarized the current research status and challenges, along with the perspectives of applications in the 2D group-IV metal chalcogenides.

Optical beam shifts in graphene and single-layer boron-nitride.

Optical beam shifts from a freestanding 2D atomic crystal are investigated. In contrast with a 3D crystal, the magnitude of the Goos-Hänchen shift depends on the surface susceptibility of the crystal and not on the wavelength of the incident light beam. The surface conductivity of the atomically thin crystal is less important in this context because it enters in the expression of the shifts only as a second-order parameter. In analogy to a 3D crystal, the magnitudes of the Imbert-Fedorov shift and of the angular shifts depend, respectively, on the wavelength and on the square of the beam angular aperture.

Dual-Gate Velocity-Modulated Transistor Based on Black Phosphorus

The layered semiconductor black phosphorus has attracted attention as a 2D atomic crystal that can be prepared in ultra-thin layers for operation as field effect transistors. Despite the susceptibility of black phosphorus to photo-oxidation, improvements to the electronic quality of black phosphorus devices has culminated in the observation of the quantum Hall effect. In this work, we demonstrate the room temperature operation of a dual gated black phosphorus transistor operating as a velocity modulated transistor, whereby modification of hole density distribution within a black phosphorus quantum well leads to a two-fold modulation of hole mobility. Simultaneous modulation of Schottky barrier resistance leads to a four-fold modulation of transcon- ductance at a fixed hole density. Our work explicitly demonstrates the critical role of charge density distribution upon charge carrier transport within 2D atomic crystals.

Nonlinear optical response of a two-dimensional atomic crystal.

The theory of Bloembergen and Pershan for the light waves at the boundary of nonlinear media is extended to a nonlinear two-dimensional (2D) atomic crystal, i.e., a single planar atomic lattice, placed between linear bulk media. The crystal is treated as a zero-thickness interface, a real 2D system. Harmonic waves emanate from it. Generalization of the laws of reflection and refraction give the direction and the intensity of the harmonic waves. As a particular case that contains all the essential physical features, second-order harmonic generation is considered. The theory, due to its simplicity that stems from the special character of a single planar atomic lattice, is able to elucidate and explain the rich experimental details of harmonic generation from a 2D atomic crystal.

Oxygen intercalation under hexagonal boron nitride (h-BN) on Pt(111)

The interface between a two-dimensional (2D) atomic crystal and a metal surface can be regarded as a nanoreactor, in which molecule adsorption and catalytic reactions may occur. In this work, we demonstrate that oxygen intercalation and desorption occur at the interface between hexagonal boron nitride (h-BN) overlayer and Pt(111) surface by using near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), photoemission electron microscopy, and low-energy electron microscopy. Furthermore, CO oxidation under the h-BN cover was also observed by NAP-XPS. The present results indicate that the nanospace under the 2D cover can be used for surface reactions, in which novel surface chemistry may be induced by the nanoconfinement effect.

Two-Dimensional Atomic Crystals: Paving New Ways for Nanoelectronics

Two-dimensional (2D) atomic crystals are attractive for use in next-generation nanoelectronics, due to their unique performances, which may lead to the resolution of the technological and fundamental challenges in semiconductor industry. Based on the introduction of 2D atomic crystal-based transistors and ambipolar behavior, the review presents a brief summary of 2D atomic crystal integration circuits, including memory, logic gate, amplifier, inverter, oscillator, mixer, switch and modulator. The devices show promising performances for the application in future nanoelectronics. In particular, the 2D atomic crystals, such as graphene, demonstrate good compatibility with the existing semiconductor process. The quaternary digital modulations have been achieved with flexible and transparent all-graphene circuits. Moreover, the heterojunction based on 2D atomic crystals may enable new devices beyond conventional field-effect transistors. The results make us be optimistic that practical 2D atomic crystal technologies with complex functionality will be achieved in the near future. Therefore, 2D atomic crystals are paving new ways for nanoelectronics.

Dirac cones in two-dimensional systems: from hexagonal to square lattices

The influence of lattice symmetry on the existence of Dirac cones was investigated for two distinct systems: a general two-dimensional (2D) atomic crystal containing two atoms in each unit cell and a 2D electron gas (2DEG) under a periodic muffin-tin potential. A criterion was derived under a tight-binding approximation for the existence of Dirac cones in the atomic crystal. When the transfer hoppings are assumed to be single functions of the distance between atoms, it was shown that the probability of observing Dirac cones in the atomic crystal gradually decreases before being reduced to zero when the lattice changes from hexagonal to square. For a 2DEG with full square symmetry, a Dirac point exists at the Brillouin zone corners, where the energy dispersion is parabolic not linear. These results suggest that conventional Dirac fermions (such as those in graphene) are difficult to achieve in a square lattice with full symmetry (wallpaper group p4mm).

Translational–rotational interaction in the dynamics and thermodynamics of a 2D atomic crystal with a molecular impurity

The interaction between the rotational degrees of freedom of a diatomic molecular impurity and the phonon excitations of a two-dimensional atomic matrix commensurate with a substrate is investigated theoretically. It is shown that the translational–rotational interaction changes the form of the rotational kinetic energy operator as compared to the corresponding expression for a free rotator, and also renormalizes the parameters of the crystal field without altering in its initial form. The contribution of the impurity rotational degrees of freedom to the low-temperature heat capacity for a dilute solution of diatomic molecules in an atomic two-dimensional matrix is calculated. The possibility of experimental observation of the predicted effects is discussed.