High-Throughput Computational Screening of All-MXene Metal-Semiconductor Junctions for Schottky-Barrier-Free Contacts with Weak Fermi-Level Pinning.

Van der Waals (vdW) metal-semiconductor junctions (MSJs) exhibit huge potential to reduce the contact resistance and suppress the Fermi-level pinning (FLP) for improving the device performance, but they are limited by optional (2D) metals with a wide range of work functions. Here a new class of vdW MSJs entirely composed of atomically thin MXenes is reported. Using high-throughput first-principles calculations, highly stable 80 metals and 13 semiconductors are screened from 2256 MXene structures. The selected MXenes cover a broad range of work functions (1.8-7.4 eV) and bandgaps (0.8-3 eV), providing a versatile material platform for constructing all-MXene vdW MSJs. The contact type of 1040 all-MXene vdW MSJs based on Schottky barrier heights (SBHs) is identified. Unlike conventional 2D vdW MSJs, the formation of all-MXene vdW MSJs leads to interfacial polarization, which is responsible for the FLP and deviation of SBHs from the prediction of Schottky-Mott rule. Based on a set of screening criteria, six Schottky-barrier-free MSJs with weak FLP and high carrier tunneling probability (>50%) are identified. This work offers a new way to realize vdW contacts for the development of high-performance electronic and optoelectronic devices.

Ultrafast nucleation and growth of high-quality monolayer MoSe2 crystals via vapor-liquid-solid mechanism.

The controlled production of two-dimensional atomically thin transition metal dichalcogenides (TMDs) is fundamentally important for their device applications. However, the synthesis of large-area and high-quality TMD monolayers remains a challenge due to the lack of sufficient understanding of growth mechanisms, especially for the chemical vapor deposition (CVD). Here we report molten-salt assisted CVD growth of highly crystalline MoSe2 monolayers via a novel vapor-liquid-solid (VLS) mechanism. Our results show that the growth rate of the VLS-grown monolayer MoSe2 is about 40 times faster than that of MoSe2 grown via the vapor-solid (VS) mechanism, which makes the fabrication of 100 µm domains for ∼2 min and a uniform monolayer film within 5 min. The ultrafast growth of monolayer MoSe2 crystals benefits from the synergic effect of one-dimensional VLS growth and two-dimensional VS edge expansion. Moreover, these MoSe2 monolayers exhibit high crystal quality and enhanced photoluminescence due to efficient Se-vacancy repairing by the doping of halogen atoms. These findings provide a new understanding of MoSe2 growth and open up an opportunity for the rapid synthesis of high-quality TMD monolayers and heterostructures.

Intriguing electronic and optical properties of two-dimensional Janus transition metal dichalcogenides.

Atomically thin Janus transition metal dichalcogenides (JTMDs) with an asymmetric structure have emerged as a new class of intriguing two-dimensional (2D) semiconductor materials. Using state-of-the-art density functional theory (DFT) calculations, we systematically investigate the structural, electronic, and optical properties of JTMD monolayers and heterostructures. Our calculated results indicate that the JTMD monolayers suffer from a bending strain but present high thermodynamic stability. All of them are semiconductors with a band-gap range from 1.37 to 1.96 eV. They possess pronounced optical absorption in the visible-light region and cover a large range of carrier mobilities from 28 to 606 cm2 V-1 s-1, indicating strong anisotropic characteristics. Significantly, some monolayer JTMDs (e.g., WSSe and WSeTe) exhibit superior mobilities than conventional TMD monolayers, such as MoS2. Moreover, the absolute band-edge positions of the JTMD monolayers are higher than the water redox potential, and most JTMD heterostructures have a type-II band alignment that contributes to the separation of carriers. Our work suggests that the 2D JTMD monolayers are promising for nanoelectronic, optoelectronic, and photocatalytic applications.

Hierarchical MoO3/SnS2 core-shell nanowires with enhanced electrochemical performance for lithium-ion batteries.

Two-dimensional (2D) tin disulfide (SnS2) is a promising anode material for lithium-ion batteries (LIBs) because of its high theoretical capacity. The main challenges associated with the SnS2 electrodes are the poor cycling stability and low rate capability due to structural degradation in the discharge/charge process. Here, a facile two-step synthesis method is developed to fabricate hierarchical MoO3/SnS2 core-shell nanowires, where ultrathin SnS2 nanosheets are vertically anchored on MoO3 nanobelts to induce a heterointerface. Benefiting from the unique structural and compositional characteristics, the hierarchical MoO3/SnS2 core-shell nanowires exhibit excellent electrochemical performance and deliver a high reversible capacity of 504 mA h g-1 after 100 stable cycles at a current density of 100 mA g-1, which is far superior to the MoO3 and SnS2 electrodes. An analysis of lithiation dynamics based on ab initio molecular dynamics simulations demonstrates that the formation of a hierarchical MoO3/SnS2 core-shell heterostructure can effectively suppress the rapid dissociation of shell-layer SnS2 nanosheets via the interfacial coupling effect and the central MoO3 backbone can trap and support the polysulfide in the discharge/charge process. The results are responsible for the high storage capacity and rate capability of MoO3/SnS2 electrode materials. This work provides a novel design strategy for constructing high-performance electrodes for LIBs.

Two-dimensional silicene nucleation on a Ag(111) surface: structural evolution and the role of surface diffusion.

The structural evolution of planar Si clusters and the nucleation mechanism of silicene in the initial stages of silicene epitaxial growth on a Ag(111) surface are studied by using ab initio calculations and two-dimensional nucleation theory. The ground-state SiN clusters (1 ≤ N ≤ 25) on the Ag(111) surface are found to undergo a significant structural transition from non-hexagonal plane structures to fully-hexagonal ones at N = 22, which is a crucial step for growing a high-quality silicene nanosheet. Furthermore, important parameters for controlling silicene growth, including the diffusion barriers of Si clusters, nucleation barrier, nucleus size, and nucleation rate are explored. Compared to graphene nucleation on transition-metal (TM) surfaces, the low diffusion barrier of Si atoms and the low nucleation barrier are responsible for the rapid nucleation of silicene on a Ag(111) surface. Our calculations demonstrate that silicene should be synthesized at a relatively low growth temperature (~500 K) in order to reduce the defect density. The results can be successfully applied to explain the broad experimental observations where the growth temperature of silicene is below 550 K.

Phase separation induced by Au catalysts in ternary InGaAs nanowires.

We report a novel phase separation phenomenon observed in the growth of ternary In(x)Ga(1-x)As nanowires by metalorganic chemical vapor deposition. A spontaneous formation of core-shell nanowires is investigated by cross-sectional transmission electron microscopy, revealing the compositional complexity within the ternary nanowires. It has been found that for In(x)Ga(1-x)As nanowires high precursor flow rates generate ternary In(x)Ga(1-x)As cores with In-rich shells, while low precursor flow rates produce binary GaAs cores with ternary In(x)Ga(1-x)As shells. First-principle calculations combined with thermodynamic considerations suggest that this phenomenon is due to competitive alloying of different group-III elements with Au catalysts, and variations in elemental concentrations of group-III materials in the catalyst under different precursor flow rates. This study shows that precursor flow rates are critical factors for manipulating Au catalysts to produce nanowires of desired composition.

Enhancement of the accuracy of the simplified modal method for designing a subwavelength triangular grooves grating.

The validity and accuracy of the simplified modal method for a highly efficient transmission subwavelength triangular grating are fully and quantitatively evaluated by a comparison of diffraction efficiencies predicted from the modal method to exact results calculated by a rigorous coupled wave analysis. The larger errors are revealed in smaller periods and in lower groove depths. More importantly, with the consideration of the reflection loss of the two propagating modes, the accuracy of the simplified modal method is significantly enhanced. The calculated diffraction efficiencies are in good agreement with the results of the vector method. This enhanced simplified modal method can be effectively used in the design of a shallower subwavelength grating. It is important to note that the consideration of the modal reflection loss can be applicable to any dielectric diffraction structure, e.g., the rectangular grating, in which the accuracy of the simplified modal method could be excellently improved to more exactly design a grating.

Strain driven enhancement of ferroelectricity and magnetoelectric effect in multiferroic tunnel junction.

The strain effect on the ferroelectric and magnetoelectric coupling in multiferroic tunnel junction (MFTJ) Co/BaTiO3/Co has been investigated systematically by using first-principles calculations within density functional theory. It is found that both in-plane compressive strain and uniaxial tensile strain lead to the enhancement of ferroelectric polarization stability and intensity of magnetoelectric coupling in the MFTJ. There is a transition from the paraelectric phase to the ferroelectric phase for the BaTiO3 layer in MFTJ when the loaded in-plane compressive strain increases up to -2.8% and the corresponding average ferroelectric polarization is about 0.13 C m(-2). Meanwhile, the calculated surface magnetoelectric coefficients increase with increasing in-plane compressive strain. Similar phenomena have been also observed in the case of uniaxial tensile strain implemented in MFTJ. The results suggest that the ferroelectric polarization and magnetoelectric coupling in multiferroic tunnel junctions can be controlled by strain and we expect that this study can provide a theoretical basis for the design of spintronic devices.

Molecular sieving of semiconductive NTU-9 coatings on titanium dioxide nanowire arrays: Augmented yet selective photoelectrochemical response enabled by boosting charge separation and transfer in confined space.

Radial heterostructures with titanium dioxide (TiO2) nanowire as core and NTU-9 as shell are synthesized via a surfactant-free approach based on the favorable bonding of linkers with TiO2 nanowire. Relative to the traditional growth strategy of surface modification, the thin NTU-9 shell with ordered arrangement of two-dimensional networks is uniformly formed on the sidewalls of TiO2 nanowire through the orientational growth process. Using the core-shell nanowire arrays as photoanodes, wide-range light absorption and high charge carrier separation efficiency are achieved due to the conjugation of NTU-9, leading to enhanced water oxidation performance in photoelectrochemical (PEC) water splitting. Under appropriately low applied potentials, the photogenerated holes are preferable to accumulate at TiO2/NTU-9/electrolyte three-phase interface and thus the long-range ordered NTU-9 shell can also serve as a size-exclusion filter to improve selectivity toward molecules of different sizes. Consequently, the TiO2/NTU-9 core-shell nanowire array exhibits an augmented and selective PEC response for small size molecules (e.g.,H2O2) at a very low potential (-0.25 V vs Ag/AgCl), outperforming the pure TiO2 nanowire array and the counterpart with a grain-boundary-rich NTU-9 shell that is prepared by pretreatment of the TiO2 nanowires with PVP functionalization.

One-step cladding metal oxide nanowires with a carbon-dots-embedded ZnO amorphous layer toward boosted photoelectrochemical water oxidation.

An effective method was proposed for constructing carbon dots (CDs)-sensitized multijunction composite photoelectrodes via one-step cladding a CDs-embedded ZnO amorphous overlayer on vertically aligned metal oxide nanowires. This strategy involved the double role of hexamethylenetetramine (HMTA) in the ethylene glycol (EG) solvent mixed with a controllable trace amount of water. In the water-deficient synthetic system, a limited portion of HMTA served as the pH buffer and hydroxyl source to force the hydrolytic process of zinc ions for the production of ZnO. The precipitated ZnO clusters were instantly capped by EG molecules through the activated alkoxidation reaction, and further crosslinked into an amorphous network surrounding the individual nanowires. Meanwhile, the excess HMTA was simultaneously depleted as the precursor for producing CDs in the EG solution through thermal condensation, which were packed in the gradually formed aggregates. We revealed that a CDs-embedded amorphous ZnO overlayer with an appropriate proportion of ingredient could be tailored through an optimal tradeoff between hydrolysis and condensation of HMTA. Benefiting from the synergy of the amorphous ZnO layer and the embedded CDs, the multijunction composite photoanodes exhibited significantly improved PEC performance and stability for water oxidation.

Phase-Controllable Growth of Air-Stable SnS Nanostructures for High-Performance Photodetectors with Ultralow Dark Current.

The epitaxial growth of low-dimensional tin chalcogenides SnX (X = S, Se) with a controlled crystal phase is of particular interest since it can be utilized to tune optoelectronic properties and exploit potential applications. However, it still remains a great challenge to synthesize SnX nanostructures with the same composition but different crystal phases and morphologies. Herein, we report a phase-controlled growth of SnS nanostructures via physical vapor deposition on mica substrates. The phase transition from α-SnS (Pbnm) nanosheets to ß-SnS (Cmcm) nanowires can be tailored by the reduction of growth temperature and precursor concentration, which originates from a delicate competition between SnS-mica interfacial coupling and phase cohesive energy. The phase transition from the α to ß phase not only greatly improves the ambient stability of SnS nanostructures but also leads to the band gap reduction from 1.03 to 0.93 eV, which is responsible for fabricated ß-SnS devices with an ultralow dark current of 21 pA at 1 V, an ultrafast response speed of ≤14 µs, and broadband spectra response from the visible to near-infrared range under ambient condition. A maximum detectivity of the ß-SnS photodetector arrives at 2.01 × 108 Jones, which is about 1 or 2 orders of magnitude larger than that of α-SnS devices. This work provides a new strategy for the phase-controlled growth of SnX nanomaterials for the development of highly stable and high-performance optoelectronic devices.

Domain nucleation kinetics and polarization-texture-dependent electronic properties in two-dimensional α-In2Se3 ferroelectrics.

Two-dimensional (2D) ferroelectric semiconductors, such as α-In2Se3 with switchable spontaneous polarization and superior optoelectronic properties, exhibit large potential for functional device applications. The electric transport properties and device performance of 2D α-In2Se3 are strongly sensitive to the ferroelectric domain structures and polarization textures, but they are rarely explored at the atomic scale. Herein, by a combination of first-principles calculations and a developed domain switching theory, we report the domain nucleation kinetics and polarization-texture dependent electronic properties in α-In2Se3 ferroelectrics. Our calculated results reveal that the reversed domains characterized by armchair boundaries tend to form triangular or stripped shape. The energy barrier for propagating domain boundaries is ∼1.42 eV and can be reduced by loading external electric field, which is responsible for driving the evolution of domain structures. Moreover, the domain switching leads to notable changes in the band gap and carrier spatial distribution of α-In2Se3 monolayer, resulting in higher electric resistance of multi-polarization domain structures than that of single-polarization state. The domain structures of multilayer α-In2Se3 follow a layer-by-layer switching mechanism, which causes the transition of electronic structures from self-doped p-n junctions to type-II semiconductor homojunctions. This study not only provides an in-depth insight into the domain switching mechanisms of α-In2Se3 but also opens up the possibility to tailor their electronic and transport properties.

Magic carbon clusters in the chemical vapor deposition growth of graphene.

Ground-state structures of supported C clusters, C(N) (N = 16, ..., 26), on four selected transition metal surfaces [Rh(111), Ru(0001), Ni(111), and Cu(111)] are systematically explored by ab initio calculations. It is found that the core-shell structured C(21), which is a fraction of C(60) possessing three isolated pentagons and C(3v) symmetry, is a very stable magic cluster on all these metal surfaces. Comparison with experimental scanning tunneling microscopy images, dI/dV curves, and cluster heights proves that C(21) is the experimentally observed dominating C precursor in graphene chemical vapor deposition (CVD) growth. The exceptional stability of the C(21) cluster is attributed to its high symmetry, core-shell geometry, and strong binding between edge C atoms and the metal surfaces. Besides, the high barrier of two C(21) clusters' dimerization explains its temperature-dependent behavior in graphene CVD growth.

Transport properties of graphene nanoribbon-based molecular devices.

The electronic and transport properties of an edge-modified prototype graphene nanoribbon (GNR) slice are investigated using density functional theory and Green's function theory. Two decorating functional group pairs are considered, such as hydrogen-hydrogen and NH(2)-NO(2) with NO(2) and NH(2) serving as a donor and an acceptor, respectively. The molecular junctions consist of carbon-based GNR slices sandwiched between Au electrodes. Nonlinear I-V curves and quantum conductance have been found in all the junctions. With increasing the source-drain bias, the enhancement of conductance is quantized. Several key factors determining the transport properties such as the electron transmission probabilities, the density of states, and the component of Frontier molecular orbitals have been discussed in detail. It has been shown that the transport properties are sensitive to the edge type of carbon atoms. We have also found that the accepter-donor functional pairs can cause orders of magnitude changes of the conductance in the junctions.

The finite-size effect on the transport properties in edge-modified graphene nanoribbon-based molecular devices.

The size-dependence on the electronic and transport properties of the molecular devices of the edge-modified graphene nanoribbon (GNR) slices is investigated using density-functional theory and Green's function theory. Two edge-modifying functional group pairs are considered. Energy gap is found in all the GNR slices. The gap shows an exponential decrease with increasing the slice size of two vertical orientations in the two edge terminated cases, respectively. The tunneling probability and the number of conducting channel decreases with increasing the GNR-slices size in the junctions. The results indicate that the acceptor-donor pair edge modulation can improve the quantum conductance and decrease the finite-size effect on the transmission capability of the GNR slice-based molecular devices.

Towards ultra small noble metal nanoparticles: testing Jellium model for ligand protected copper and silver M13 core nanoparticles.

The bare M and ligand-protected nanoparticles M(25)(SR) and M(13)(PR)(10)Cl (M = Au, Ag, Cu) are investigated using the density functional theory. There are strong interactions between the metal core atoms and the ligands. It is found that the electronic structures agree well with the Jellium model for gold and copper nanoparticles. The superatoms's S and P orbitals are shown. However for silver ones, as the adding of the ligands, the S orbital of the nanoparticle disappears. The binding energy of these nanoparticles are also obtained by our calculation. The Au nanoparticles are most stable, the Cu ones take second place, and the Ag ones are the third stable. Our results could be essential for further understanding of the properties of ligand-protected isolated superatoms.

Effect of electrodes on geometric and transport properties of the graphene-based nanomolecular devices.

Graphene-based nanomolecular devices are formed by connecting one of the prototype molecular materials of graphene nanoribbons to two Au electrodes. The geometric structure and electronic properties are calculated by using density functional theory. Basing on the optimized structure and the electronic distributions, we obtain the transport properties of the devices by using the Green's functional method. It is found that that the geometry structures of the molecule and the transport properties are sensitive to the distance between source and drain electrodes. With increasing the distances, the curvature radius of the atomic plane is increased, and the deformation energy is decreased. The current versus voltage curves have almost same threshold voltage with different distances between the electrodes. The transmission probability, the density of states and the external bias voltage play important role in determining the transport properties of the molecular devices.

Intrinsic Polarization-Induced Enhanced Ferromagnetism and Self-Doped p-n Junctions in CrBr3/GaN van der Waals Heterostructures.

Two-dimensional (2D) ferromagnetic (FM) semiconductors with a high Curie temperature and tunable electronic properties are a long-term pursuing target for the development of high-performance spin-dependent optoelectronic devices. Herein, on the basis of density functional theory calculations, we report a new strategy to tune the Curie temperature and electronic structures of a ferromagnetic CrBr3 monolayer through the formation of CrBr3/GaN van der Waals heterostructures. Our calculated results demonstrate that the Curie temperature and band alignment of CrBr3/GaN heterostructures strongly depend on the thickness and polarization direction of the GaN layer. The combination of the CrBr3 monolayer with N-terminated GaN nanosheets leads to enhanced FM coupling via superexchange interactions between the Cr-t2g and Cr-eg orbitals, consequently resulting in a Curie temperature of CrBr3 of up to 67 K. Moreover, self-doped p-n junctions can be naturally formed in the heterostructures without additional modulation of external fields. The enhanced FM coupling and self-doping effect in the heterostructures are associated with the intrinsic polarization of the GaN layer that drives interfacial electron transfers from GaN to CrBr3. Therefore, this work not only offers an efficient scheme to boost the Curie temperature of the CrBr3 monolayer but also opens up a new route to realize nonvolatile van der Waals p-n junctions.

Strong intrinsic room-temperature ferromagnetism in freestanding non-van der Waals ultrathin 2D crystals.

Control of ferromagnetism is of critical importance for a variety of proposed spintronic and topological quantum technologies. Inducing long-range ferromagnetic order in ultrathin 2D crystals will provide more functional possibility to combine their unique electronic, optical and mechanical properties to develop new multifunctional coupled applications. Recently discovered intrinsic 2D ferromagnetic crystals such as Cr2Ge2Te6, CrI3 and Fe3GeTe2 are intrinsically ferromagnetic only below room temperature, mostly far below room temperature (Curie temperature, ~20-207 K). Here we develop a scalable method to prepare freestanding non-van der Waals ultrathin 2D crystals down to mono- and few unit cells (UC) and report unexpected strong, intrinsic, ambient-air-robust, room-temperature ferromagnetism with TC up to ~367 K in freestanding non-van der Waals 2D CrTe crystals. Freestanding 2D CrTe crystals show comparable or better ferromagnetic properties to widely-used Fe, Co, Ni and BaFe12O19, promising as new platforms for room-temperature intrinsically-ferromagnetic 2D crystals and integrated 2D devices.

2D-VN2 MXene as a novel anode material for Li, Na and K ion batteries: Insights from the first-principles calculations.

Developing two-dimensional (2D) materials as anode materials have been proved a promising approach to significantly improve the charge storage performances of alkali metal ion. Herein, we investigate mono-layered VN2 as an anode material in Li, Na and K ion batteries. Firstly, the high stability of 2D-VN2 has been demonstrated via calculating the phonon spectra. 2D-VN2 is capable of delivering high capacities of 678.8, 339.4 and 1357.6 mAh g-1 in Li+, K+ and Na+ storage, respectively. In addition, the metallic properties and corresponding high electrical conductivity and low diffusion barriers of 201.1 meV for Li atoms, 34.7 meV for K atoms and 84.1 meV for Na atoms on VN2 surface, indicating good capacity and the superior rate performances of alkali metal atoms migration on VN2. The calculated average voltage of Li, Na and K are respectively 0.81 V, 0.29 V and 0.77 V, suggesting a promising voltage behavior compared with other 2D materials.