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Electric currents have the intriguing ability to induce magnetization in nonmagnetic crystals with sufficiently low crystallographic symmetry. Some associated phenomena include the non-linear anomalous Hall effect in polar crystals and the nonreciprocal directional dichroism in chiral crystals when magnetic fields are applied. In this work, we demonstrate that the same underlying physics is also manifested in the electronic tunneling process between the surface of a nonmagnetic chiral material and a magnetized scanning probe. In the paramagnetic but chiral metallic compound Co1/3NbS2, the magnetization induced by the tunneling current is shown to become detectable by its coupling to the magnetization of the tip itself. This results in a contrast across different chiral domains, achieving atomic-scale spatial resolution of structural chirality. To support the proposed mechanism, we used first-principles theory to compute the chirality-dependent current-induced magnetization and Berry curvature in the bulk of the material. Our demonstration of this magnetochiral tunneling effect opens up an avenue for investigating atomic-scale variations in the local crystallographic symmetry and electronic structure across the structural domain boundaries of low-symmetry nonmagnetic crystals.
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Zinc-nitrate batteries can integrate energy supply, ammonia electrosynthesis, and sewage disposal into one electrochemical device. However, current zinc-nitrate batteries still severely suffer from the limited energy density and poor rechargeability. Here, we report the synthesis of tetraphenylporphyrin (tpp)-modified heterophase (amorphous/crystalline) rhodium-copper alloy metallenes (RhCu M-tpp). Using RhCu M-tpp as a bifunctional catalyst for nitrate reduction reaction (NO3RR) and ethanol oxidation reaction in neutral solution, a highly rechargeable and low-overpotential zinc-nitrate/ethanol battery is successfully constructed, which exhibits outstanding energy density of 117364.6 Wh kg-1cat, superior rate capability, excellent cycling stability of ~400 cycles, and potential ammonium acetate production. Ex/in situ experimental studies and theoretical calculations reveal that there is a molecule-metal relay catalysis in NO3RR over RhCu M-tpp that significantly facilitates the ammonia selectivity and reaction kinetics via a low energy barrier pathway. This work provides an effective design strategy of multifunctional metal-based catalysts toward the high-performance zinc-based hybrid energy systems.
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Engineering the valley index is essential and highly sought for valley physics, but currently, it is exclusively based on the paradigm of the challenging ferrovalley with spin-orientation reversal under a magnetic field. Here, an alternative strategy, i.e., the so-called ferroelectrovalley, is proposed to tackle the insurmountable spin-orientation reversal, which reverses the valley index with the feasible ferroelectricity. Using symmetry arguments and the tight-binding model, the C2z rotation is unveiled to be able to take the place of time reversal for operating the valley index in two-dimensional multiferroic kagome lattices, which enables a ferroelectricity-engineered valley index, thereby generating the concept of a ferroelectrovalley. Based on first-principles calculations, this concept is further demonstrated in the breathing kagome lattice of single-layer Ti3Br8, wherein ferroelectricity couples with the breathing process. These findings open a new direction for valleytronics and 2D materials research.
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We show that the origin of the antiferromagnetic coupling in spin-1 triangulene chains, which were recently synthesized and measured by Mishra et al. ( Nature 2021, 598, 287-292), originates from a superexchange mechanism. This process, mediated by intertriangulene states, opens the possibility to control parameters in the effective bilinear-biquadratic spin model. We start from the derivation of an effective tight-binding model for triangulene chains using a combination of tight-binding and Hartree-Fock methods fitted to hybrid density functional theory results. Next, correlation effects are investigated within the configuration interaction method. Our low-energy many-body spectrum for NTr = 2 and NTr = 4 triangulene chains agree well with the bilinear-biquadratic spin-1 chain antiferromagnetic model when indirect coupling processes and superexchange coupling between triangulene spins are taken into account.
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Photovoltaic efficiency in solar cells is hindered by many unwanted effects. Radiative channels (emission of photons) sometimes mediated by nonradiative ones (emission of phonons) are principally responsible for the decrease in exciton population before charge separation can take place. One such mechanism is electron-hole recombination at surfaces or defects where the in-gap edge states serve as the nonradiative channels. In topological insulators (TIs), which are rarely explored from an optoelectronics standpoint, we show that their characteristic surface states constitute a nonradiative decay channel that can be exploited to generate a protected photovoltaic current. Focusing on two-dimensional TIs, and specifically for illustration purposes on a Bi(111) monolayer, we obtain the transition rates from the bulk excitons to the edge states. By breaking the appropriate symmetries of the system, one can induce an edge charge accumulation and edge currents under illumination, demonstrating the potential of TI nanoribbons for photovoltaics.
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Hyperbolic polaritons have been attracting increasing interest for applications in optoelectronics, biosensing, and super-resolution imaging. Here, we report the in-plane hyperbolic exciton polaritons in monolayer black-arsenic (B-As), where hyperbolicity arises strikingly from two exciton resonant peaks. Remarkably, the presence of two resonances at different momenta makes overall hyperbolicity highly tunable by strain, as the two exciton peaks can be merged into the same frequency to double the strength of hyperbolicity as well as light absorption under a 1.5% biaxial strain. Moreover, the frequency of the merged hyperbolicity can be further tuned from 1.35 to 0.8 eV by an anisotropic biaxial strain. Furthermore, electromagnetic numerical simulation reveals a strain-induced hyperbolicity, as manifested in a topological transition of iso-frequency contour of exciton polaritons. The good tunability, large exciton binding energy, and strong light absorption exhibited in the hyperbolic monolayer B-As make it highly suitable for nanophotonics applications under ambient conditions.
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Two-dimensional (2D) materials have shown great potential in applications as transistors, where thermal dissipation becomes crucial because of the increasing energy density. Although the thermal conductivity of 2D materials has been extensively studied, interactions between nonequilibrium electrons and phonons, which can be strong when high electric fields and heat current coexist, are not considered. In this work, we systematically study the electron drag effect, where nonequilibrium electrons impart momenta to phonons and influence the thermal conductivity, in 2D semiconductors using ab initio simulations. We find that, at room temperature, electron drag can significantly increase thermal conductivity by decreasing phonon-electron scattering in 2D semiconductors while its impact in three-dimensional semiconductors is negligible. We attribute this difference to the large electron-phonon scattering phase space and larger contribution to thermal conductivity by drag-active phonons. Our work elucidates the fundamental physics underlying coupled electron-phonon transport in materials of various dimensionalities.
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Rare-earth diantimondes exhibit coupling between structural and electronic orders, which are tunable under pressure and temperature. Here we present the discovery of a new polymorph of LaSb2 stabilized in thin films synthesized using molecular beam epitaxy. Using diffraction, electron microscopy, and first-principles calculations we identify a YbSb2-type monoclinic lattice as a yet-uncharacterized stacking configuration. The material hosts superconductivity with a Tc = 2 K, which is enhanced relative to the bulk ambient phase, and a long superconducting coherence length of 1730 Å. This result highlights the potential thin film growth has in stabilizing novel stacking configurations in quasi-two-dimensional compounds with competing layered structures.
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Polymorph engineering involves the manipulation of material properties through controlled structural modification and is a candidate technique for creating unique two-dimensional transition metal dichalcogenide (TMDC) nanodevices. Despite its promise, polymorph engineering of magnetic TMDC monolayers has not yet been demonstrated. Here we grow FeSe2 monolayers via molecular beam epitaxy and find that they have great promise for magnetic polymorph engineering. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we find that FeSe2 monolayers predominantly display a 1T' structural polymorph at 5 K. Application of voltage pulses from an STM tip causes a local, reversible transition from the 1T' phase to the 1T phase. Density functional theory calculations suggest that this single-layer structural phase transition is accompanied by a magnetic transition from an antiferromagnetic to a ferromagnetic configuration. These results open new possibilities for creating functional magnetic devices with TMDC monolayers via polymorph engineering.
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Manipulating the polarization of light at the nanoscale is key to the development of next-generation optoelectronic devices. This is typically done via waveplates using optically anisotropic crystals, with thicknesses on the order of the wavelength. Here, using a novel ultrafast electron-beam-based technique sensitive to transient near fields at THz frequencies, we observe a giant anisotropy in the linear optical response in the semimetal WTe2 and demonstrate that one can tune the THz polarization using a 50 nm thick film, acting as a broadband wave plate with thickness 3 orders of magnitude smaller than the wavelength. The observed circular deflections of the electron beam are consistent with simulations tracking the trajectory of the electron beam in the near field of the THz pulse. This finding offers a promising approach to enable atomically thin THz polarization control using anisotropic semimetals and defines new approaches for characterizing THz near-field optical response at far-subwavelength length scales.
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Valleytronics, i.e., the manipulation of the valley degree of freedom, offers a promising path for energy-efficient electronics. One of the key milestones in this field is the room-temperature manipulation of the valley information in thick-layered material. Using scanning photocurrent microscopy, we achieve this milestone by observing a geometrically dependent circular photocurrent in a few-layer molybdenum disulfide (MoS2) under normal incidence. Such an observation shows that the system symmetry is lower than that of bulk MoS2 material, preserving the optical chirality-valley correspondence. Moreover, the circular photocurrent polarity can be reversed by applying electrical bias. We propose a model where the observed photocurrent results from the symmetry breaking and the built-in field at the electrode-sample interface. Our results show that the valley information is still retained even in thick-layered MoS2 at room temperature and opens up new opportunities for exploiting the valley index through interface engineering in multilayer valleytronics devices.
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Stacking monolayer semiconductors creates moiré patterns, leading to correlated and topological electronic phenomena, but measurements of the electronic structure underpinning these phenomena are scarce. Here, we investigate the properties of the conduction band in moiré heterobilayers of WS2/WSe2 using submicrometer angle-resolved photoemission spectroscopy with electrostatic gating. We find that at all twist angles the conduction band edge is the K-point valley of the WS2, with a band gap of 1.58 ± 0.03 eV. From the resolved conduction band dispersion, we deduce an effective mass of 0.15 ± 0.02 me. Additionally, we observe replicas of the conduction band displaced by reciprocal lattice vectors of the moiré superlattice. We argue that the replicas result from the moiré potential modifying the conduction band states rather than final-state diffraction. Interestingly, the replicas display an intensity pattern with reduced 3-fold symmetry, which we show implicates the pseudo vector potential associated with in-plane strain in moiré band formation.
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Fluorite mineral holds significant importance because of its optoelectronic properties and wide range of applications. Here, we report the successful exfoliation of bulk fluorite ore (calcium fluoride, CaF2) crystals into atomically thin two-dimensional fluoritene (2D CaF2) using a highly scalable liquid-phase exfoliation method. The microscopic and spectroscopy characterizations show the formation of (111) plane-oriented 2D CaF2 sheets with exfoliation-induced material strain due to bond breaking, leading to the changes in lattice parameter. Its potential role in electrocatalysis is further explored for deeper insight, and a probable mechanism is also discussed. The 2D CaF2 with long-term stability shows overpotential values of 670 and 770 mV vs RHE for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), respectively, at 10 mA cm-2. Computational simulations demonstrate the unique "direct-indirect" band gap switching with odd and even numbers of layers. Current work offers new avenues for exploring the structural and electrochemical properties of 2D CaF2 and its potential applicability.
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Revealing low-dimensional material growth dynamics is critical for crystal growth engineering. However, in a practical high-temperature growth system, the crystal growth process is a black box because of the lack of heat-resistant imaging tools. Here, we develop a heat-resistant optical microscope and embed it in a chemical vapor deposition (CVD) system to investigate two-dimensional (2D) crystal growth dynamics. This in situ optical imaging CVD system can tolerate temperatures of ≤900 °C with a spatial resolution of â¼1 µm. The growth of monolayer MoS2 crystals was studied as a model for 2D crystal growth. The nucleation and growth process have been imaged. Model analysis and simulation have revealed the growth rate, diffusion coefficient, and spatial distribution of the precursor. More importantly, a new vertex-kink-ledge model has been suggested for monolayer crystal growth. This work provides a new technique for in situ microscopic imaging at high temperatures and fundamental insight into 2D crystal growth.
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The nature of ion-ion interactions in electrolytes confined to nanoscale pores has important implications for energy storage and separation technologies. However, the physical effects dictating the structure of nanoconfined electrolytes remain debated. Here we employ machine-learning-based molecular dynamics simulations to investigate ion-ion interactions with density functional theory level accuracy in a prototypical confined electrolyte, aqueous NaCl within graphene slit pores. We find that the free energy of ion pairing in highly confined electrolytes deviates substantially from that in bulk solutions, observing a decrease in contact ion pairing but an increase in solvent-separated ion pairing. These changes arise from an interplay of ion solvation effects and graphene's electronic structure. Notably, the behavior observed from our first-principles-level simulations is not reproduced even qualitatively with the classical force fields conventionally used to model these systems. The insight provided in this work opens new avenues for predicting and controlling the structure of nanoconfined electrolytes.
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Herein, we report a high-density dual-structure single-atom catalyst (SAC) by creating a large number of vacancies of O and Ti in two-dimensional (2D) Ti3C2 to immobilize Pt atoms (SA Pt-Ti3C2). The SA Pt-Ti3C2 showed excellent performance toward the pH-universal electrochemical hydrogen evolution reaction (HER) and multimodal sensing. For HER catalysis, compared to the commercial 20 wt % Pt/C, the Pt mass activities of SA Pt-Ti3C2 at the overpotentials of â¼30 and 110 mV in acid and alkaline media are 45 and 34 times higher, respectively. More importantly, during the alkaline HER process, an interesting synergetic effect between Pt-C and Pt-Ti sites that dominated the Volmer and Heyrovsky steps, respectively, was revealed. Moreover, the SA Pt-Ti3C2 catalyst exhibited high sensitivity (0.62-2.65 µA µM-1) and fast response properties for the multimodal identifications of ascorbic acid, dopamine, uric acid, and nitric oxide under the assistance of machine learning.
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An interesting question is whether chalcogen atoms can emulate the role of carbon or boron elements stabilized between two transition metal layers, as observed in MXenes or MBenes. Here, we predict a new family of two-dimensional ternary compounds M4XY2 (where M = Pd, Y, Zr, etc.; X = S, Se, Te; and Y = Cl, Br, I), named M-chalcogene. Through first-principles calculations, we reveal diverse physical properties in these compounds, including superconducting, topological, and magnetic characteristics, where the bilayer transition metals play crucial roles. Moreover, the expected helical edge states and superconducting transition temperatures in Pd4SCl2 can be finely tuned by strains. Additionally, the Ti4SCl2 is predicted to be a topological insulator and shows promise as a gas sensor candidate for certain exotic gases. Our findings expand two-dimensional material families and provide promising platforms for diverse physical phenomena with efficient tunability by external stimuli for various applications.
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Piezoelectricity has been widely explored for nanoelectromechanical applications, yet its working modes are mainly limited in polar directions. Here we discover the intrinsic electro-mechanical response in crystal materials that is transverse to the conventional polarized direction, which is named unconventional piezoelectricity. A Hall-like mechanism is proposed to interpret unconventional piezoelectricity as charge polarization driven by a built-in electric field for systems with asymmetric Berry curvature distributions. Density functional theory simulations and statistical analyses justify such a mechanism and confirm that unconventional piezoelectricity is a general property for various two-dimensional materials with spin splitting or valley splitting. An empirical formula is derived to connect the conventional and unconventional piezoelectricity. The extended understanding of the piezoelectric tensor in quantum materials opens an opportunity for applications in multidirectional energy conversion, broadband operation, and multifunctional sensing.
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Nonvolatile multistate manipulation of two-dimensional (2D) magnetic materials holds promise for low dissipation, highly integrated, and versatile spintronic devices. Here, utilizing density functional theory calculations and Monte Carlo simulations, we report the realization of nonvolatile and multistate control of topological magnetism in monolayer CrI3 by constructing multiferroic heterojunctions with quadruple-well ferroelectric (FE) materials. The Pt2Sn2Te6/CrI3 heterojunction exhibits multiple magnetic phases upon modulating FE polarization states of FE layers and interlayer sliding. These magnetic phases include Bloch-type skyrmions and ferromagnetism, as well as a newly discovered topological magnetic structure. We reveal that the Dzyaloshinskii-Moriya interaction (DMI) induced by interfacial coupling plays a crucial role in magnetic skyrmion manipulation, which aligns with the Fert-Levy mechanism. Moreover, a regular magnetic skyrmion lattice survives when removing a magnetic field, demonstrating its robustness. The work sheds light on an effective approach to nonvolatile and multistate control of 2D magnetic materials.
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The reduced dimensionality and interfacial effects in magnetic nanostructures open the feasibility to tailor magnetic ordering. Here, we report the synthesis of ultrathin metallic Co2Si nanoplates with a total thickness that is tunable to 2.2 nm. The interfacial magnetism coupled with the highly anisotropic nanoplate geometry leads to strong perpendicular magnetic anisotropy and robust hard ferromagnetism at room temperature, with a Curie temperature (TC) exceeding 950 K and a coercive field (HC) > 4.0 T at 3 K and 8750 Oe at 300 K. Theoretical calculations suggest that ferromagnetism originates from symmetry breaking and undercoordinated Co atoms at the Co2Si and SiO2 interface. With protection by the self-limiting intrinsic oxide, the interfacial ferromagnetism of the Co2Si nanoplates exhibits excellent environmental stability. The controllable growth of ambient stable Co2Si nanoplates as 2D hard ferromagnets could open exciting opportunities for fundamental studies and applications in Si-based spintronic devices.