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 improve 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.
This theoretical study examines the formation, structure, and stability of two of the most ordered nanothreads produced yet, those derived from furan and thiophene. The energetic consequences and ...activation barriers of the first two steps of oligomerization via a Diels–Alder mechanism were examined. The ca. 20 GPa difference in the synthetic pressures (lower for furan) is explainable in terms of the greater loss of aromaticity by the thiophene. The effects of pressure on the reaction profiles, operating through a volume decrease along the reaction coordinate, are illustrated. The interesting option of polymerization proceeding in one or two directions opens up the possibility of polymers with opposing, cumulative dipole moments. The computed activation volumes are consistently more negative for furan, in accordance with the lower onset pressure of furan polymerization. The energetics of three ordered polymer structures were examined. The syn polymer, with all O/S atoms on the same side, if not allowed to distort, is at a high energy relative to the other two due to the O/S lone pair repulsion, understandably greater for S than for O at the 2.8/2.6 Å separation. Set free, the syn isomers curve or arch in two- or three-dimensional (helical) ways, whose energetics are traced in detail. The syn polymer can also stabilize itself by twisting into zig-zag or helical energy minima. The release of strain in a linear thread as the pressure is relaxed to 1 atm, with consequent thread curving, is a likely mechanism for the observed loss of the crystalline order in the polymer as it is returned to ambient pressure.
Individual monolayers of metal dichalcogenides are atomically thin two-dimensional crystals with attractive physical properties different from those of their bulk counterparts. Here we describe the ...direct synthesis of WS2 monolayers with triangular morphologies and strong room-temperature photoluminescence (PL). The Raman response as well as the luminescence as a function of the number of S–W–S layers is also reported. The PL weakens with increasing number of layers due to a transition from direct band gap in a monolayer to indirect gap in multilayers. The edges of WS2 monolayers exhibit PL signals with extraordinary intensity, around 25 times stronger than that at the platelet’s center. The structure and chemical composition of the platelet edges appear to be critical for PL enhancement.
Acoustic actuation of bioinspired microswimmers is experimentally demonstrated. Microswimmers are fabricated in situ in a microchannel. Upon acoustic excitation, the flagellum of the microswimmer ...oscillates, which in turn generates linear or rotary movement depending on the swimmer design. The speed of these bioinspired microswimmers is tuned by adjusting the voltage amplitude applied to the acoustic transducer. Simple microfabrication and remote actuation are promising for biomedical applications.
Abstract
Double-resonance Raman scattering is a sensitive probe to study the electron-phonon scattering pathways in crystals. For semiconducting two-dimensional transition-metal dichalcogenides, the ...double-resonance Raman process involves different valleys and phonons in the Brillouin zone, and it has not yet been fully understood. Here we present a multiple energy excitation Raman study in conjunction with density functional theory calculations that unveil the double-resonance Raman scattering process in monolayer and bulk MoS
2
. Results show that the frequency of some Raman features shifts when changing the excitation energy, and first-principle simulations confirm that such bands arise from distinct acoustic phonons, connecting different valley states. The double-resonance Raman process is affected by the indirect-to-direct bandgap transition, and a comparison of results in monolayer and bulk allows the assignment of each Raman feature near the
M
or
K
points of the Brillouin zone. Our work highlights the underlying physics of intervalley scattering of electrons by acoustic phonons, which is essential for valley depolarization in MoS
2
.
A defect-controlled approach for the nucleation and epitaxial growth of WSe2 on hBN is demonstrated. The WSe2 domains exhibit a preferred orientation of over 95%, leading to a reduced density of ...inversion domain boundaries (IDBs) upon coalescence. First-principles calculations and experimental studies as a function of growth conditions and substrate pretreatment confirm that WSe2 nucleation density and orientation are controlled by the hBN surface defect density rather than thermodynamic factors. Detailed transmission electron microscopy analysis provides support for the role of single-atom vacancies on the hBN surface that trap W atoms and break surface symmetry leading to a reduced formation energy for one orientation of WSe2 domains. Through careful control of nucleation and extended lateral growth time, fully coalesced WSe2 monolayer films on hBN were achieved. Low-temperature photoluminescence (PL) measurements and transport measurements of back-gated field-effect transistor devices fabricated on WSe2/hBN films show improved optical and electrical properties compared to films grown on sapphire under similar conditions. Our results reveal an important nucleation mechanism for the epitaxial growth of van der Waals heterostructures and demonstrate hBN as a superior substrate for single-crystal transition-metal dichalcogenide (TMD) films, resulting in a reduced density of IDBs and improved properties. The results motivate further efforts focused on the development of single crystal hBN substrates and epilayers for synthesis of wafer-scale single crystal TMD films.
Selective actuation of a single microswimmer from within a diverse group would be a first step toward collaborative guided action by a group of swimmers. Here we describe a new class of microswimmer ...that accomplishes this goal. Our swimmer design overcomes the commonly-held design paradigm that microswimmers must use non-reciprocal motion to achieve propulsion; instead, the swimmer is propelled by oscillatory motion of an air bubble trapped within the swimmer's polymer body. This oscillatory motion is driven by the application of a low-power acoustic field, which is biocompatible with biological samples and with the ambient liquid. This acoustically-powered microswimmer accomplishes controllable and rapid translational and rotational motion, even in highly viscous liquids (with viscosity 6,000 times higher than that of water). And by using a group of swimmers each with a unique bubble size (and resulting unique resonance frequencies), selective actuation of a single swimmer from among the group can be readily achieved.
Grain boundaries in two-dimensional crystals are usually thought to separate distinct crystallites and as such they must either form closed loops or terminate at the boundary of a sample. However, ...when an atomically thin two-dimensional crystal grows on a substrate of nonzero Gaussian curvature, it can develop finite-length grain boundaries that terminate abruptly within a monocrystalline domain. We show that by properly designing the substrate topography, these grain boundaries can be placed at desired locations and at specified misfit angles, as the thermodynamic ground state of a two-dimensional (2D) system bound to a substrate. Compared against the hypothetical competition of growing defectless 2D materials on a Gaussian-curved substrate with consequential fold development or detachment from the substrate, the nucleation and formation of finite-length grain boundaries can be made energetically favorably given sufficient substrate adhesion on the order of tens of meV/Å2 for typical 2D materials. New properties specific to certain grain boundary geometries, including magnetism and metallicity, can thus be engineered into 2D crystals through topographic design of their substrates.
Abstract
The rapid discovery of two-dimensional (2D) van der Waals (vdW) quantum materials has led to heterostructures that integrate diverse quantum functionalities such as topological phases, ...magnetism, and superconductivity. In this context, the epitaxial synthesis of vdW heterostructures with well-controlled interfaces is an attractive route towards wafer-scale platforms for systematically exploring fundamental properties and fashioning proof-of-concept devices. Here, we use molecular beam epitaxy to synthesize a vdW heterostructure that interfaces two material systems of contemporary interest: a 2D ferromagnet (1T-CrTe
2
) and a topological semimetal (ZrTe
2
). We find that one unit-cell (u.c.) thick 1T-CrTe
2
grown epitaxially on ZrTe
2
is a 2D ferromagnet with a clear anomalous Hall effect. In thicker samples (12 u.c. thick CrTe
2
), the anomalous Hall effect has characteristics that may arise from real-space Berry curvature. Finally, in ultrathin CrTe
2
(3 u.c. thickness), we demonstrate current-driven magnetization switching in a full vdW topological semimetal/2D ferromagnet heterostructure device.
Graphite intercalation compounds are formed by inserting guest molecules or ions between sp(2)-bonded carbon layers. These compounds are interesting as synthetic metals and as precursors to graphene. ...For many decades it has been thought that graphite intercalation must involve host-guest charge transfer, resulting in partial oxidation, reduction or covalent modification of the graphene sheets. Here, we revisit this concept and show that graphite can be reversibly intercalated by non-oxidizing Brønsted acids (phosphoric, sulfuric, dichloroacetic and alkylsulfonic acids). The products are mixtures of graphite and first-stage intercalation compounds. X-ray photoelectron and vibrational spectra indicate that the graphene layers are not oxidized or reduced in the intercalation process. These observations are supported by density functional theory calculations, which indicate a dipolar interaction between the guest molecules and the polarizable graphene sheets. The intercalated graphites readily exfoliate in dimethylformamide to give suspensions of crystalline single- and few-layer graphene sheets.
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