Monolayer Limit Research Articles

Competing Coulomb and electron\u2013phonon interactions in NbS2

The interplay of Coulomb and electron–phonon interactions with thermal and quantum fluctuations facilitates rich phase diagrams in two-dimensional electron systems. Layered transition metal dichalcogenides hosting charge, excitonic, spin and superconducting order form an epitomic material class in this respect. Theoretical studies of materials like NbS2 have focused on the electron–phonon coupling, whereas the Coulomb interaction, particularly strong in the monolayer limit, remained essentially untouched. Here, we analyze the interplay of short- and long-range Coulomb as well as electron–phonon interactions in NbS2 monolayers. The combination of these interactions causes electronic correlations that are fundamentally different to what would be expected from the interaction terms separately. The fully interacting electronic spectral function resembles the non-interacting band structure but with appreciable broadening. An unexpected coexistence of strong charge and spin fluctuations puts NbS2 close to spin and charge order, suggesting monolayer NbS2 as a platform for atomic scale engineering of electronic quantum phases.

Strongly enhanced exciton-phonon coupling in two-dimensional WSe2

The recently emerging laminar transition metal dichalcogenides provide an unprecedented platform for exploring fascinating layer-dependent properties. Determining the dependence of exciton-phonon coupling (EPC) on dimensionality would set a foundation for these exotic thickness-dependent phenomena. Here we report the observation of layer-dependent EPC between the ${A}_{1g}(\mathrm{\ensuremath{\Gamma}})$ phonon and A\ensuremath{'} exciton in $\mathrm{WS}{\mathrm{e}}_{2}$ down to the monolayer limit. Our results uncover that the strength of EPC increases dramatically with a descent of layer thickness. Compared with their bulk counterparts, the strength of EPC in monolayer $\mathrm{WS}{\mathrm{e}}_{2}$ is enhanced by nearly an order of magnitude. Furthermore, our work demonstrates that the giant EPC in the monolayer plays a prominent role in the exotic interlayer EPC of $\mathrm{WS}{\mathrm{e}}_{2}$/boron nitride heterostructures. The gigantic EPC in the two-dimensional limit provides a firm basis for understanding and manipulating the peculiar phenomena and novel optoelectronic applications based on atomically thin $\mathrm{WS}{\mathrm{e}}_{2}$.

Structural stability and vibrational analysis of beryllium sulfide BeS from the bulk to the (n,0) nanotubes. An ab initio description

Beryllium sulfide (BeS) in different forms from molecule, bulk, monolayer (h-BeS), to the single-walled nanotube obtained by wrapping the h-BeS monolayer along the (n,0) hexagonal lattice vector for n varying from n = 6 to 64, has been examined. Density functional theory (DFT) with an all electron basis set and the hybrid DFT/B3LYP level have been applied to compute energetic and geometrical, electronic and vibrational, elastic and piezoelectric properties, where the trend towards the hexagonal monolayer (h-BeS) in the limit of large tube radius is obtained. The vibrational properties including Raman spectra and polarizabilities are evaluated via the Coupled Perturbed Hartree–Fock and Kohn–Sham (CPHF/KS) computational schemes. For the first time, the IR vibrational modes at higher tube diameter and their convergence to the h-BeS monolayer limit are reported where the vibrational and electronic contributions to both perpendicular and parallel components of polarizability tensor are additionally discussed. For the (n,0) BeS nanotube family, three ranges of IR active phonon modes are determined. The first one located in the 0–300 cm−1frequency domain, goes regularly to zero when the tube diameter increases. Both the second (300–400 cm−1) and the third (700–800 cm−1) ones tend smoothly with different slope, towards the two optical vibrational modes of the h-BeS layer. These theoretical models can be extended to investigate further issues, such as the effect caused by the addition of a dopant, the influence of the substitutional fraction of nanotube atoms and the interaction of molecules outside and/or inside of the nanotube.

Colloquium : Excitons in atomically thin transition metal dichalcogenides

Atomically thin materials such as graphene and monolayer transition metal dichalcogenides (TMDs) exhibit remarkable physical properties resulting from their reduced dimensionality and crystal symmetry. The family of semiconducting transition metal dichalcogenides is an especially promising platform for fundamental studies of two-dimensional (2D) systems, with potential applications in optoelectronics and valleytronics due to their direct band gap in the monolayer limit and highly efficient light-matter coupling. A crystal lattice with broken inversion symmetry combined with strong spin-orbit interactions leads to a unique combination of the spin and valley degrees of freedom. In addition, the 2D character of the monolayers and weak dielectric screening from the environment yield a significant enhancement of the Coulomb interaction. The resulting formation of bound electron-hole pairs, or excitons, dominates the optical and spin properties of the material. Here we review recent progress in our understanding of the excitonic properties in monolayer TMDs and lay out future challenges. We focus on the consequences of the strong direct and exchange Coulomb interaction, discuss exciton-light interaction and effects of other carriers and excitons on electron-hole pairs in TMDs. Finally, the impact on valley polarization is described and the tuning of the energies and polarization observed in applied electric and magnetic fields is summarized.

Room Temperature Intrinsic Ferromagnetism in Epitaxial Manganese Selenide Films in the Monolayer Limit.

Monolayer van der Waals (vdW) magnets provide an exciting opportunity for exploring two-dimensional (2D) magnetism for scientific and technological advances, but the intrinsic ferromagnetism has only been observed at low temperatures. Here, we report the observation of room temperature ferromagnetism in manganese selenide (MnSe x) films grown by molecular beam epitaxy (MBE). Magnetic and structural characterization provides strong evidence that, in the monolayer limit, the ferromagnetism originates from a vdW manganese diselenide (MnSe2) monolayer, while for thicker films it could originate from a combination of vdW MnSe2 and/or interfacial magnetism of α-MnSe(111). Magnetization measurements of monolayer MnSe x films on GaSe and SnSe2 epilayers show ferromagnetic ordering with a large saturation magnetization of ∼4 Bohr magnetons per Mn, which is consistent with the density functional theory calculations predicting ferromagnetism in monolayer 1T-MnSe2. Growing MnSe x films on GaSe up to a high thickness (∼40 nm) produces α-MnSe(111) and an enhanced magnetic moment (∼2×) compared to the monolayer MnSe x samples. Detailed structural characterization by scanning transmission electron microscopy (STEM), scanning tunneling microscopy (STM), and reflection high energy electron diffraction (RHEED) reveals an abrupt and clean interface between GaSe(0001) and α-MnSe(111). In particular, the structure measured by STEM is consistent with the presence of a MnSe2 monolayer at the interface. These results hold promise for potential applications in energy efficient information storage and processing.

Prediction of manganese trihalides as two-dimensional Dirac half-metals

The recent discovery of intrinsic ferromagnetism in two-dimensional (2D) van der Waals crystals down to the monolayer limit has sparked intense interest due to their potential applications in spintronics. Here, using first-principles calculations we predict that the 2D pristine ${\mathrm{MnX}}_{3}$ (X = F, Cl, Br, I) is a family of intrinsic Dirac half-metals characterized by a band structure with an unusually large gap in one spin channel and a Dirac cone in the other with carrier mobilities comparable to those in graphene. We demonstrate that the ${\mathrm{MnX}}_{3}$ are dynamically and thermodynamically stable up to high temperatures, and exhibit large magnetic moments of about $4\phantom{\rule{4pt}{0ex}}{\ensuremath{\mu}}_{B}$ per ${\mathrm{Mn}}^{3+}$ ion, high Curie temperatures, and large in-plane magnetic anisotropy energy. In addition, the gap opening induced by the spin-orbit coupling drives the lighter systems into the quantum anomalous Hall state. The combination of these unique properties renders this class of 2D ferromagnets a promising platform for high efficiency spintronic applications.

Superior Electro-Oxidation and Corrosion Resistance of Monolayer Transition Metal Disulfides.

Physics of monolayer and few-layer transition metal dichalcogenides (TMDs) and chemistry of few-layer TMDs have been well studied in recent years in the context of future electronic, optoelectronic, and energy harvesting applications. However, what has escaped the attention of the scientific community is the unique chemistry of monolayer TMDs. It has been demonstrated that the basal plane of multilayer TMDs is chemically inert, whereas edge sites are chemically active. In this article, we experimentally demonstrate that the edge reactivity of the TMDs can be significantly impeded at the monolayer limit through monolayer/substrate interaction, thus making the monolayers highly resistant to electrooxidation and corrosion. In particular, we found that few-layer flakes of MoS2 and WS2 exfoliated on conductive TiN substrates are readily corroded beyond a certain positive electrode potential, while monolayer remnants are left behind unscathed. The electrooxidation resistance of monolayers was confirmed using a plethora of characterization techniques including atomic force microscope (AFM) imaging, Raman spectroscopy, photoluminescence (PL) mapping, scanning/transmission electron microscope (S/TEM) imaging, and selected area electron diffraction (SAED). It is believed that strong substrate monolayer interaction compared to the relatively weak interlayer van der Waals interaction is responsible for the superior monolayers chemical stability in highly corrosive oxidizing environments. Our findings could pave the way for the implementation of monolayer transition metal disulfides as superior anticorrosion coating which can have a significant socioeconomic impact.

Structural distortions in monolayers of binary semiconductors

We examine the structural properties of free standing II-VI and III-V semiconductors at the monolayer limit within first principle density functional theory calculations. A non-polar buckled structure was found to be favoured over a polar buckled structure. While an obvious reason for this may be traced to the contribution from dipole dipole interactions present in the polar structure which would destabilize it with respect to the nonpolar structure, Coulomb interactions between electrons on the cations and anions are found to be the reason for the nonpolar structure to be favoured. A route to tune the Coulomb interaction between the electrons on the cations and anions is through biaxial tensile strain. This allows for a planar graphitic phase in CdS to be stabilized at just 2\% tensile strain. Strain also shifts the valence band maximum from the $\Gamma$ point to the K point opening up opportunities for exploring spin-valley physics in these materials.

Chemical vapor transport synthesis of a selenium-based two-dimensional material

Selenium-based layered materials, and in particular transition-metal diselenides (TMDSs), have intriguing properties in the monolayer limit. Materials such as MoSe$_{2}$, WSe$_{2}$, and NbSe$_{2}$ display striking features such as spin-valley coupling at the valence-band edges and offer great potential for optoelectronics applications. Although a dozen of other TMDSs have been realized or proposed, whether two-dimensional chalcogens are possible or not is still an open challenge. In this work, we show the chemical vapor transport synthesis of a novel, atomically thin selenium-based material on oxidized silicon substrates. This new member of the two-dimensional materials family has a unique Raman spectrum similar to that of bulk selenium and has an optical gap of $\sim $1.57 eV at room temperature determined by the photoluminescence. No transition metals are found in the stoichiometry of the crystals. Analysis of high-resolution transmission electron micrographs of the monolayers reveals a distinctive set of hexagonal spots indicating a sixfold symmetry of the lattice. Atomic force microscopy measurements show the monolayer thickness to be $\sim $0.75 nm.

A progressive metal–semiconductor transition in two-faced Janus monolayer transition-metal chalcogenides

Breaking the symmetry in the out-of-plane direction in two-dimensional materials to trigger distinctive electronic properties has long been predicted. Inspired by the recent progress in the experimental synthesis of a sandwiched S-Mo-Se structure (Janus SMoSe) at the monolayer limit [Zhang et al., ACS Nano, 2017, 11, 8192-8198], we investigate the transport and electronic structure of two-faced XMoY monolayers (X, Y = O, S, Se and Te) through first-principles calculations. It is found that all the monolayers are semiconductors except OMoTe, which is metallic. Interestingly, the "parents" of OMoTe (MoO2 and MoTe2) are both semiconductors. Further analysis shows that it is the out-of-plane asymmetry-induced strain that results in the metal-semiconductor transition between Janus OMoTe and its parents. By increasing the ratio of O atoms in one face of MoTe2, a progressive decreasing trend of the bandgap, as well as the transition to metallic, is found. In addition, a transition from the direct band gap semiconductor to the indirect one is also observed in the process. This could be used as an effective way to precisely control electronic structures, e.g., the bandgap. Different from other methods, this method uses the intrinsic features of the material, which can persist without the need of additional equipment. Moreover, such a modulating method is expected to be extended to many other transition-metal chalcogenides, showing great application potential.

Chemical vapor growth and delamination of α-RuCl3 nanosheets down to the monolayer limit.

The 2D layered honeycomb magnet α-ruthenium(iii) chloride (α-RuCl3) is a promising candidate to realize a Kitaev spin model. As alteration of physical properties on the nanoscale is additionally intended, new synthesis approaches to obtain phase pure α-RuCl3 nanocrystals have been audited. Thermodynamic simulations of occurring gas phase equilibria were performed and optimization of synthesis conditions was achieved based on calculation results. Crystal growth succeeded via chemical vapor transport (CVT) in a temperature gradient of 973 K to 773 K on YSZ substrates. Single crystal sheets of high crystallinity with heights ≤30 nm were obtained via pure CVT. The crystal properties were characterized by means of optical and electron microscopy, AFM, SAED, micro-Raman and XPS proving their composition, morphology, crystallinity and phase-purity. A highlight of our study is the successful individualization of nanocrystals and the delamination of nanosheets on YSZ substrates down to the monolayer limit (≤1 nm) which was realized by means of substrate exfoliation and ultrasonication in a very reproducible way.

First-principles study of Na-intercalated bilayer NbSe2 : Suppressed charge-density wave and strain-enhanced superconductivity

Layered ${\mathrm{NbSe}}_{2}$ is a metallic layered transition metal dichalcogenide (TMD) that has attracted much interest for the coexistence of superconductivity and charge-density wave (CDW) down to the monolayer limit. Here we report first-principles calculations of the lattice dynamics, electronic structure, and electron-phonon coupling of Na-intercalated bilayer ${\mathrm{NbSe}}_{2}$. We show that upon the Na atom intercalation, the CDW instability in the bilayer ${\mathrm{NbSe}}_{2}$ can be effectively suppressed, accompanied by the removal of the soft phonon modes at ${\mathbf{q}}_{\mathrm{CDW}}=\frac{2}{3}\mathrm{\ensuremath{\Gamma}}M$. The underlying mechanism for this phenomenon is that a large electron doping from the intercalated Na contracts the Fermi surface of bilayer ${\mathrm{NbSe}}_{2}$ and reduces the electron-phonon coupling at ${\mathbf{q}}_{\mathrm{CDW}}$. In spite of the disappearance of CDW, the superconductivity still survives in the ${\mathrm{NbSe}}_{2}$ intercalate, with a predicted superconducting transition temperature ${T}_{c}$ of 3 K. Moreover, we find that the biaxial compressive strain can greatly increase density of states near the Fermi surface and soften characteristic phonons contributing to superconductivity, leading to an increase of ${T}_{c}$ by more than 100% at a low strain level of 3%. Our results would have significant implications for tuning CDW and superconductivity in ${\mathrm{NbSe}}_{2}$ and other metallic TMD materials.

Nature of carrier injection in metal/2D-semiconductor interface and its implications for the limits of contact resistance

Monolayers of transition metal dichalcogenides (TMDCs) exhibit excellent electronic and optical properties. However, the performance of these two-dimensional (2D) devices are often limited by the large resistance offered by the metal contact interface. Till date, the carrier injection mechanism from metal to 2D TMDC layers remains unclear, with widely varying reports of Schottky barrier height (SBH) and contact resistance (Rc), particularly in the monolayer limit. In this work, we use a combination of theory and experiments in Au and Ni contacted monolayer MoS2 device to conclude the following points: (i) the carriers are injected at the source contact through a cascade of two potential barriers - the barrier heights being determined by the degree of interaction between the metal and the TMDC layer; (ii) the conventional Richardson equation becomes invalid due to the multi-dimensional nature of the injection barriers, and using Bardeen-Tersoff theory, we derive the appropriate form of the Richardson equation that describes such composite barrier; (iii) we propose a novel transfer length method (TLM) based SBH extraction methodology, to reliably extract SBH by eliminating any confounding effect of temperature dependent channel resistance variation; (iv) we derive the Landauer limit of the contact resistance achievable in such devices. A comparison of the limits with the experimentally achieved contact resistance reveals plenty of room for technological improvements.

Mixed oxides on rutile TiO2(011): Cr2O3 and Cu2O

The authors investigate the formation of ultrathin oxides on rutile TiO2(011) single crystal surfaces by scanning tunneling microscopy and photoemission techniques in view of the role of substrate orientation for the formation of special oxide species and films. The authors observe that the (011) orientation of rutile facilitates the stabilization of ordered atomic-scale Cu+ species under weak oxidizing conditions. In contrast, clustering is observed on the (110) surface prepared under the same conditions. For chromium deposition in an oxidizing environment growth of an epitaxial but twinned Cr2O3 film with (1-102) orientation is observed. High crystalline order is maintained to the ultrathin monolayer limit. X-ray photoelectron spectroscopy suggests some diffusion of Ti3+ species into Cr2O3 films while the surface of Cr2O3 appears to be reducible by vacuum annealing to ∼300 °C. An increased photocatalytic activity for decomposition of methyl orange solution is measured for TiO2(011) surfaces modified with a submonolayer film of chromia while for thicker Cr2O3 films the photocatalytic activity decreases again.

Charged defects in two-dimensional semiconductors of arbitrary thickness and geometry: Formulation and application to few-layer black phosphorus

Energy evaluation of charged defects is tremendously important in two-dimensional (2D) semiconductors for the industrialization of 2D electronic devices because of its close relation with the corresponding type of conductivity and its strength. Although the method to calculate the energy of charged defects in single-layer one-atom-thick systems of equilateral unit-cell geometry has recently been proposed, few-layer 2D semiconductors are more common in device applications. As it turns out, one may not apply the one-layer formalism to multilayer cases without jeopardizing accuracy. Here, we generalize the approach to 2D systems of arbitrary cell geometry and thickness and use few-layer black phosphorus to illustrate how defect properties, mainly group-VI substitutional impurities, are affected. Within the framework of density functional theory, we show that substitutional Te $(\mathrm{T}{\mathrm{e}}_{\mathrm{P}})$ is the best candidate for $n$-type doping, and as the thickness increases, the ionization energy is found to decrease monotonically from 0.67 eV (monolayer) to 0.47 eV (bilayer) and further to 0.33 eV (trilayer). Although these results show the ineffectiveness of the dielectric screening at the monolayer limit, they also show how it evolves with increasing thickness whereby setting a new direction for the design of 2D electronics. The proposed method here is generally suitable to all the 2D materials regardless of their thickness and geometry.

Janus Monolayer Transition-Metal Dichalcogenides.

The crystal configuration of sandwiched S-Mo-Se structure (Janus SMoSe) at the monolayer limit has been synthesized and carefully characterized in this work. By controlled sulfurization of monolayer MoSe2, the top layer of selenium atoms is substituted by sulfur atoms, while the bottom selenium layer remains intact. The structure of this material is systematically investigated by Raman, photoluminescence, transmission electron microscopy, and X-ray photoelectron spectroscopy and confirmed by time-of-flight secondary ion mass spectrometry. Density functional theory (DFT) calculations are performed to better understand the Raman vibration modes and electronic structures of the Janus SMoSe monolayer, which are found to correlate well with corresponding experimental results. Finally, high basal plane hydrogen evolution reaction activity is discovered for the Janus monolayer, and DFT calculation implies that the activity originates from the synergistic effect of the intrinsic defects and structural strain inherent in the Janus structure.

Strain engineering of atomic and electronic structures of few-monolayer-thick GaN

Two-dimensional (2D) semiconductors possess the potential to ultimately minimize the size of devices and concomitantly drastically reduce the corresponding energy consumption. In addition, materials in their atomic-scale limit often possess properties different from their bulk counterparts paving the way to conceptually novel devices. While graphene and 2D transition-metal dichalcogenides remain the most studied materials, significant interest also exists in the fabrication of atomically thin structures from traditionally 3D semiconductors such as GaN. While in the monolayer limit GaN possesses a graphenelike structure and an indirect band gap, it was recently demonstrated that few-layer GaN acquires a Haeckelite structure in the direction of growth with an effectively direct gap. In this work, we demonstrate the possibility of strain engineering of the atomic and electronic structure of few-monolayer-thick GaN structures, which opens new avenues for their practical application in flexible nanoelectronics and nano-optoelectronics. Our simulations further suggest that due to the weak van der Waals-like interaction between a substrate and an overlayer, the use of a ${\mathrm{MoS}}_{2}$ substrate may be a promising route to fabricate few-monolayer Haeckelite GaN experimentally.

Emergence of Dirac-like bands in the monolayer limit of epitaxial Ge films on Au(1 1 1)

After the discovery of Dirac fermions in graphene, it has become a natural question to ask whether it is possible to realize Dirac fermions in other two-dimensional (2D) materials as well. In this work, we report the discovery of multiple Dirac-like electronic bands in ultrathin Ge films grown on Au(1 1 1) by angle-resolved photoelectron spectroscopy. By tuning the thickness of the films, we are able to observe the evolution of their electronic structure when passing through the monolayer limit. Our discovery may signify the synthesis of germanene, a 2D honeycomb structure made of Ge, which is a promising platform for exploring exotic topological phenomena and enabling potential applications.

Magneto photoluminescence measurements of tungsten disulphide monolayers

Layered transition-metal dichalcogenides have attracted great interest in the last few years. Thinned down to the monolayer limit they change from an indirect band structure to a direct band gap in the visible region. Due to the monolayer thickness the inversion symmetry of the crystal is broken and spin and valley are coupled to each other. The degeneracy between the two equivalent valleys, K and K′, respectively, can be lifted by applying an external magnetic field. Here, we present photoluminescence measurements of CVD-grown tungsten disulphide (WS2) monolayers at temperatures of 2 K. By applying magnetic fields up to 7 T in Faraday geometry, a splitting of the photoluminescence peaks can be observed. The magnetic field dependence of the A-exciton, the trion and three bound exciton states is discussed and the corresponding g-factors are determined.

Ising-Type Magnetic Ordering in Atomically Thin FePS3.

Magnetism in two-dimensional materials is not only of fundamental scientific interest but also a promising candidate for numerous applications. However, studies so far, especially the experimental ones, have been mostly limited to the magnetism arising from defects, vacancies, edges, or chemical dopants which are all extrinsic effects. Here, we report on the observation of intrinsic antiferromagnetic ordering in the two-dimensional limit. By monitoring the Raman peaks that arise from zone folding due to antiferromagnetic ordering at the transition temperature, we demonstrate that FePS3 exhibits an Ising-type antiferromagnetic ordering down to the monolayer limit, in good agreement with the Onsager solution for two-dimensional order-disorder transition. The transition temperature remains almost independent of the thickness from bulk to the monolayer limit with TN ∼ 118 K, indicating that the weak interlayer interaction has little effect on the antiferromagnetic ordering.