Electric Field-Modulated Magnetic Phase Transition in van der Waals CrI₃ Bilayers

Two-dimensional van der Waals (vdW) magnetic materials are well-recognized milestones toward nanostructured spintronics. An interesting example is CrI3; its magnetic states can be modulated electrically, allowing spintronics applications that are highly compatible with electronics technologies. Here, we report the electric field alone induces the interlayer antiferromagnetic-to-ferromagnetic (AFM-to-FM) phase transition in CrI3 bilayers with critical field as low as 0.12 V/Å. The AFM-FM energy difference ΔE increases with electric field and is closely related to the field-induced on-site energy difference defined as the splitting between the electronic states of the two vdW layers. Our tight-binding model fits closely with ΔE as a function of electric field and gives a consistent estimation for orbital hopping, exchange splitting, and crystal field splitting. Furthermore, a CrI3-based spin field-effect device is suggested with the spin current switched on and off solely by the electric field. These findings not only reveal the physics underlying the transition but also provide guidelines for future discovery and design

Phonon–Grain-Boundary-Interaction-Mediated Thermal Transport in Two-Dimensional Polycrystalline MoS₂

Although dislocations and grain boundaries (GBs) are ubiquitous in large-scale MoS2 samples, their interaction with phonons, which plays an important role in determining the lattice thermal conductivity of polycrystalline MoS2, remains elusive. Here, we perform a systematic study of the heat transport in two-dimensional polycrystalline MoS2 by both molecular dynamics simulation and atomic Green’s function method. Our results indicate that the thermal boundary conductance of GBs of MoS2 is in the range from 6.4 × 108 to 35.3 × 108 W m–2 K–1, which is closely correlated with the overlap between the vibrational density of states of GBs and those of the pristine lattice, as well as the GB energy. It is found that the GBs strongly scatter the phonons with frequency larger than 2 THz, accompanied by a pronounced phonon localization effect and significantly reduced phonon group velocities. Furthermore, by comparing the results from realistic polycrystalline MoS2 to those from different theoretical models, we observe that the Casimir model is broken down and detailed phonon dynamics at a specific GB should be taken into account to accurately describe the phonon transport in polycrystalline materials. Our findings will provide useful guidelines for designing efficient thermoelectric and thermal management materials based on phonon–GB interaction

Predicting Dislocations and Grain Boundaries in Two-Dimensional Metal-Disulfides from the First Principles

Guided by the principles of dislocation theory, we use the first-principles calculations to determine the structure and properties of dislocations and grain boundaries (GB) in single-layer transition metal disulfides MS₂ (M = Mo or W). In sharp contrast to other two-dimensional materials (truly planar graphene and <i>h</i>-BN), here the edge dislocations extend in third dimension, forming concave dreidel-shaped polyhedra. They include different number of homoelemental bonds and, by reacting with vacancies, interstitials, and atom substitutions, yield families of the derivative cores for each Burgers vector. The overall structures of GB are controlled by both local-chemical and far-field mechanical energies and display different combinations of dislocation cores. Further, we find two distinct electronic behaviors of GB. Typically, their localized deep-level states act as sinks for carriers but at large 60°-tilt the GB become metallic. The analysis shows how the versatile GB in MS₂ (if carefully engineered) should enable new developments for electronic and opto-electronic applications

Environment-Controlled Dislocation Migration and Superplasticity in Monolayer MoS₂

The two-dimensional (2D) transition metal dichalcogenides (TMDC, of generic formula MX₂) monolayer displays the “triple-decker” structure with the chemical bond organization much more complex than in well-studied monatomic layers of graphene or boron nitride. Accordingly, the makeup of the dislocations in TMDC permits chemical variability, depending sensitively on the equilibrium with the environment. In particular, first-principles calculations show that dislocations state can be switched to highly mobile, profoundly changing the lattice relaxation and leading to superplastic behavior. With 2D MoS₂ as an example, we construct full map for dislocation dynamics, at different chemical potentials, for both the M- and X-oriented dislocations. Depending on the structure of the migrating dislocation, two different dynamic mechanisms are revealed: either the direct rebonding (RB) mechanism where only a single metal atom shifts slightly, or generalized Stone–Wales (SW^g) rotation in which several atoms undergo significant displacements. The migration barriers for RB mechanism can be 2–4 times lower than for the SW^g. Our analyses show that within a range of chemical potentials, highly mobile dislocations could at the same time be thermodynamically favored, that is statistically dominating the overall material property. This demonstrates remarkable possibility of changing material basic property such as plasticity by changing elemental chemical potentials of the environment

Half-Metallicity in Co-Doped WSe₂ Nanoribbons

The recent development of two-dimensional transition-metal dichalcogenides in electronics and optoelelectronics has triggered the exploration in spintronics, with high demand in search for half-metallicity in these systems. Here, through density functional theory (DFT) calculations, we predict robust half-metallic behaviors in Co-edge-doped WSe₂ nanoribbons (NRs). With electrons partially occupying the antibonding state consisting of Co 3d_yz and Se 4p_z orbitals, the system becomes spin-polarized due to the defect-state-induced Stoner effect and the strong exchange splitting eventually gives rise to the half-metallicity. The half-metal gap reaches 0.15 eV on the DFT generalized gradient approximation level and increases significantly to 0.67 eV using hybrid functional. Furthermore, we find that the half-metallicity sustains even under large external strain and relatively low edge doping concentration, which promises the potential of such Co-edge-doped WSe₂ NRs in spintronics applications

Environment-Controlled Dislocation Migration and Superplasticity in Monolayer MoS₂

The two-dimensional (2D) transition metal dichalcogenides (TMDC, of generic formula MX₂) monolayer displays the “triple-decker” structure with the chemical bond organization much more complex than in well-studied monatomic layers of graphene or boron nitride. Accordingly, the makeup of the dislocations in TMDC permits chemical variability, depending sensitively on the equilibrium with the environment. In particular, first-principles calculations show that dislocations state can be switched to highly mobile, profoundly changing the lattice relaxation and leading to superplastic behavior. With 2D MoS₂ as an example, we construct full map for dislocation dynamics, at different chemical potentials, for both the M- and X-oriented dislocations. Depending on the structure of the migrating dislocation, two different dynamic mechanisms are revealed: either the direct rebonding (RB) mechanism where only a single metal atom shifts slightly, or generalized Stone–Wales (SW^g) rotation in which several atoms undergo significant displacements. The migration barriers for RB mechanism can be 2–4 times lower than for the SW^g. Our analyses show that within a range of chemical potentials, highly mobile dislocations could at the same time be thermodynamically favored, that is statistically dominating the overall material property. This demonstrates remarkable possibility of changing material basic property such as plasticity by changing elemental chemical potentials of the environment

Intrinsic Magnetism of Grain Boundaries in Two-Dimensional Metal Dichalcogenides

Grain boundaries (GBs) are structural imperfections that typically degrade the performance of materials. Here we show that dislocations and GBs in two-dimensional (2D) metal dichalcogenides MX₂ (M = Mo, W; X = S, Se) can actually <i>improve</i> the material by giving it a qualitatively new physical property: magnetism. The dislocations studied all display a substantial magnetic moment of ∼1 Bohr magneton. In contrast, dislocations in other well-studied 2D materials are typically nonmagnetic. GBs composed of pentagon–heptagon pairs interact ferromagnetically and transition from semiconductor to half-metal or metal as a function of tilt angle and/or doping level. When the tilt angle exceeds 47°, the structural energetics favor square–octagon pairs and the GB becomes an antiferromagnetic semiconductor. These exceptional magnetic properties arise from interplay of dislocation-induced localized states, doping, and locally unbalanced stoichiometry. Purposeful engineering of topological GBs may be able to convert MX₂ into a promising 2D magnetic semiconductor

Real-Time Observing Ultrafast Carrier and Phonon Dynamics in Colloidal Tin Chalcogenide van der Waals Nanosheets

Because of their earth-abundant, low-cost, and environmentally benign characteristics, two-dimensional (2D) group IV metal chalcogenides (e.g., SnSe2) with layered structures have shown great potential in optoelectronic, photovoltaic, and thermoelectric applications. However, the intrinsic motion of excited carriers and their coupling with lattice photons, which fundamentally dictates device operation and optimization, remain yet to be unraveled. Herein, we directly follow the ultrafast carrier and photon dynamics of colloidal SnSe2 nanosheets in real time using ultrafast transient absorption spectroscopy. We show ∼0.3 ps intervalley relaxation process of photoexcited energetic carriers and ∼3 ps carrier defect trapping process with a long-lived trapped carrier (∼1 ns), highlighting the importance of trapped carriers in optoelectronic devices. In addition, ultrashort laser pulse impulsively drives coherent out-of-plane lattice vibration in SnSe2, indicating strong electron–phonon coupling in SnSe2. This strong electron–phonon coupling could impose a fundamental limit on SnSe2 photovoltaic devices but benefit its thermoelectric applications