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Manipulating the chirality of the spin-polarized electronic state is pivotal for understanding many unusual quantum spin phenomena, but it has not been achieved at the single-molecule level. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we successfully manipulate the chirality of spin distribution in a triple-decker single-molecule magnet tris(phthalocyaninato)bis(terbium(III)) (Tb2Pc3), which is evaporated on a Pb(111) substrate via molecular beam epitaxy. The otherwise achiral Tb2Pc3 becomes chiral after being embedded into the self-assembled monolayer films of bis(phthalocyaninato)terbium(III) (TbPc2). The chirality of the spin distribution in Tb2Pc3 is manifested via the spatial mapping of its Kondo resonance state from its ligand orbital. Our first-principles calculations revealed that the spin and molecular chirality are associated with a small rotation followed by a structural distortion of the top Pc, consistent with the experimental observation. By constructing tailored molecular clusters with the STM tip, a single Tb2Pc3 molecule can be manipulated among achiral and differently handed chiral configurations of spin distributions reversibly. This paves the way for designing chiral spin enantiomers for fundamental studies and developing functional spintronic devices.
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Manipulating single electrons at the atomic scale is vital for mastering complex surface processes governed by the transfer of individual electrons. Polarons, composed of electrons stabilized by electron-phonon coupling, offer a pivotal medium for such manipulation. Here, using scanning tunneling microscopy and spectroscopy (STM/STS) and density functional theory (DFT) calculations, we report the identification and manipulation of a new type of polaron, dubbed van der Waals (vdW) polaron, within mono- to trilayer ultrathin films composed of Sb2O3 molecules that are bonded via vdW attractions. The Sb2O3 films were grown on a graphene-covered SiC(0001) substrate via molecular beam epitaxy. Unlike prior molecular polarons, STM imaging observed polarons at the interstitial sites of the molecular film, presenting unique electronic states and localized band bending. DFT calculations revealed the lowest conduction band as an intermolecular bonding state, capable of ensnaring an extra electron through locally diminished intermolecular distances, thereby forming an intermolecular vdW polaron. We also demonstrated the ability to generate, move, and erase such vdW polarons using an STM tip. Our work uncovers a new type of polaron stabilized by coupling with intermolecular vibrations where vdW interactions dominate, paving the way for designing atomic-scale electron transfer processes and enabling precise tailoring of electron-related properties and functionalities.
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Recent advances in creating moiré periods of two-dimensional heterostructures enable diverse and compatible tunability to modulate the conventional proximity effect involving superconductivity, magnetism, and topology. Here, by constructing a MnTe/NbSe2 heterojunction via molecular beam epitaxy growth, we report on a moiré-enhanced multiband superconductivity by low-temperature scanning tunneling microscopy/spectroscopy measurements. We observe a distinct double-gap superconducting spectrum on monolayer MnTe that is absent on the NbSe2 substrate. The subgap character exhibits a moiré-related oscillation in real space, which can be well described by an effective two-band model. The restored two-gap feature and its rapid suppression under a small magnetic field are speculated to be mediated by the moiré superlattice, which is closely related to the enhanced interband coupling strength of quasiparticle scattering. Our work paves the way for engineering proximitized properties of heterostructures by a moiré landscape with spatial modulations.
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In kagome lattice, with the emergence of Dirac cones and flat band in electronic structure, it provides a versatile ground for exploring intriguing interplay among frustrated geometry, topology and correlation. However, such engaging interest is strongly limited by available kagome materials in nature. Here we report on a synthetic strategy of constructing kagome systems via self-intercalation of Fe atoms into the van der Waals gap of FeSe2 via molecular beam epitaxy. Using low-temperature scanning tunneling microscopy, we unveil a kagome-like morphology upon intercalating a 2 × 2 ordered Fe atoms, resulting in a stoichiometry of Fe5Se8. Both the bias-dependent STM imaging and theoretical modeling calculations suggest that the kagome pattern mainly originates from slight but important reconstruction of topmost Se atoms, incurred by the nonequivalent subsurface Fe sites due to the intercalation. Our study demonstrates an alternative approach of constructing artificial kagome structures, which envisions to be tuned for exploring correlated quantum states.
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The Mott state in 1T-TaS2 is predicted to host quantum spin liquids (QSLs). However, its insulating mechanism is controversial due to complications from interlayer coupling. Here, we study the charge transfer state in monolayer 1T-NbSe2, an electronic analogue to TaS2 exempt from interlayer coupling, using spectroscopic imaging scanning tunneling microscopy and first-principles calculations. Monolayer NbSe2 surprisingly displays two types of star of David (SD) motifs with different charge transfer gap sizes, which are interconvertible via temperature variation. In addition, bilayer 1T-NbSe2 shows a Mott collapse by interlayer coupling. Our calculation unveils that the two types of SDs possess distinct structural distortions, altering the effective Coulomb energies of the central Nb orbital. Our calculation suggests that the charge transfer gap, the same parameter for determining the QSL regime, is tunable with strain. This finding offers a general strategy for manipulating the charge transfer state in related systems, which may be tuned into the potential QSL regime.
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The synthesis and integration of core-shell materials have been extensively explored in three-dimensional nanostructures, while they are hardly ever extended into the emerging two-dimensional (2D) research field. Herein, demonstrated by graphene (G) and hexagonal boron nitride (h-BN) and via a sequential chemical vapor deposition method, we succeed for the first time in synthesizing 2D h-BN-G core-shell arrays (CSA), which possess extremely high uniformity in shapes, sizes and distributions. Each of the core-shell units is composed of G ring-shaped shell internally filled with h-BN circular core. In addition, we perform simulations to further explain the self-symmetrical etching growth mechanism of the h-BN-G CSA, demonstrating its potential to be used as an efficient synthetic method suitable for other 2D CSA systems.
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Single-element polarization in low dimensions is fascinating for constructing next-generation nanoelectronics with multiple functionalities, yet remains difficult to access with satisfactory performance. Here, spectroscopic evidences are presented for the spontaneous electronic polarization in tellurium (Te) films thinned down to bilayer, characterized by low-temperature scanning tunneling microscopy/spectroscopy. The unique chiral structure and centrosymmetry-breaking character in 2D Te gives rise to sizable in-plane polarization with accumulated charges, which is demonstrated by the reversed band-bending trends at opposite polarization edges in spatially resolved spectra and conductance mappings. The polarity of charges exhibits intriguing influence on imaging the moiré superlattice at the Te-graphene interface. Moreover, the plain spontaneous polarization robustly exists for various film thicknesses, and can universally preserve against different epitaxial substrates. The experimental validations of considerable electronic polarization in Te multilayers thus provide a realistic platform for promisingly facilitating reliable applications in microelectronic devices.
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The heavy fermion physics is dictated by subtle competing exchange interactions, posing a challenge to their understanding. One-dimensional (1D) Kondo lattice model has attracted special attention in theory, because of its exact solvability and expected unusual quantum criticality. However, such experimental material systems are extremely rare. Here, we demonstrate the realization of quasi-1D Kondo lattice behavior in a monolayer van der Waals crystal NbSe2, that is driven into a stripe phase via Se-deficient line defects. Spectroscopic imaging scanning tunneling microscopy measurements and first-principles calculations indicate that the stripe-phase NbSe2 undergoes a novel charge-density wave transition, creating a matrix of local magnetic moments. The Kondo lattice behavior is manifested as a Fano resonance at the Fermi energy that prevails the entire film with a high Kondo temperature. Importantly, coherent Kondo screening occurs only in the direction of the stripes. Upon approaching defects, the Fano resonance exhibits prominent spatial 1D oscillations along the stripe direction, reminiscent of Kondo holes in a quasi-1D Kondo lattice. Our findings provide a platform for exploring anisotropic Kondo lattice behavior in the monolayer limit.
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We demonstrate a reversible chiral switching of bis(phthalocyaninato) terbium(III) molecules on an Ir(111) surface by low temperature scanning tunneling microscopy. With an azimuthal rotation of its upper phthalocyanine ligand, the molecule can be switched between a chiral and an achiral configuration actuated by respective inelastic electron tunneling and local current heating. Moreover, the molecular chiral configuration can be interchanged between left and right handedness during the switching manipulations, thereby opening up potential nanotechnological applications.
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Unraveling the magnetic order in iron chalcogenides and pnictides at atomic scale is pivotal for understanding their unconventional superconducting pairing mechanism, but is experimentally challenging. Here, by utilizing spin-polarized scanning tunneling microscopy, real-space spin contrasts are successfully resolved to exhibit atomically unidirectional stripes in Fe4 Se5 ultrathin films, the plausible closely related compound of bulk FeSe with ordered Fe-vacancies, which are grown by molecular beam epitaxy. As is substantiated by the first-principles electronic structure calculations, the spin contrast originates from a pair-checkerboard antiferromagnetic ground state with in-plane magnetization, which is modulated by a spin-lattice coupling. These measurements further identify three types of nanoscale antiferromagnetic domains with distinguishable spin contrasts, which are subject to thermal fluctuations into short-ranged patches at elevated temperatures. This work provides promising opportunities in understanding the emergent magnetic order and the electronic phase diagram for FeSe-derived superconductors.
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2D-material-based van der Waals heterostructures (vdWhs) have shown great potential in next-generation multi-functional microelectronic devices. Thanks to their sharp interface and ultrathin thickness, 2D p-n junctions with high rectification properties have been established by combining p-type monochalcogenides with n-type transition metal dichalcogenides. However, the anisotropic rectification together with the charge transfer and gate effect has not been clarified. Herein, the electrical anisotropy of p-SnS/n-MoS2 diodes was studied. Optimum ideality factors within 1.08-1.18 have been achieved for the diode with 6.6 nm thick SnS on monolayer MoS2, and a high rectification ratio of 3.1 × 104 with strong in-plane anisotropy is observed along the zigzag direction of SnS. A strong gate effect on the anisotropic series resistance has been verified and an effective tuning over the transport length of the SnS channel can be established through adjustment of the current orientation and gate voltage. A thickness-dependent minority carrier transport mechanism has also been demonstrated for the reverse drain current, and Fowler-Nordheim tunneling and direct tunneling are proposed for the increase of the reverse current of the thicker and thinner diodes, respectively. This work will provide another strategy for high-performance diodes based on vdWhs via the control of the current orientation and the gate effect.
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Polarons are entities of excess electrons dressed with local response of lattices, whose atomic-scale characterization is essential for understanding the many body physics arising from the electron-lattice entanglement, yet difficult to achieve. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we show the visualization and manipulation of single polarons in monolayer CoCl2, that are grown on HOPG substrate via molecular beam epitaxy. Two types of polarons are identified, both inducing upward local band bending, but exhibiting distinct appearances, lattice occupations and polaronic states. First principles calculations unveil origin of polarons that are stabilized by cooperative electron-electron and electron-phonon interactions. Both types of polarons can be created, moved, erased, and moreover interconverted individually by the STM tip, as driven by tip electric field and inelastic electron tunneling effect. This finding identifies the rich category of polarons in CoCl2 and their feasibility of precise control unprecedently, which can be generalized to other transition metal halides.
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Correlated states have emerged in low-dimensional systems owing to enhanced Coulomb interactions. Elucidating these states requires atomic-scale characterization and delicate control capabilities. Herein, spectroscopic imaging-scanning tunneling microscopy was employed to investigate the correlated states residing in 1D electrons of the monolayer and bilayer MoSe2 mirror twin boundary (MTB). The Coulomb energies, determined by the wire length, drive the MTB into two types of ground states with distinct respective out-of-phase and in-phase charge orders. The two ground states can be reversibly converted through a metastable zero-energy state with in situ voltage pulses, which tune the electron filling of the MTB via a polaronic process, substantiated by first-principles calculations. Our Hubbard model calculation with an exact diagonalization method reveals the ground states as correlated insulators from an on-site U-originated Coulomb interaction, dubbed the Hubbard-type Coulomb blockade effect. Our study lays a foundation for understanding and tailoring correlated physics in complex systems.
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We have performed spin-resolved measurements on a Kondo impurity in the presence of RKKY-type exchange coupling. By placing manganese phthalocyanine (MnPc) molecules on Fe-supported Pb islands, a Kondo system is devised which is exchange coupled to a magnetic substrate via conduction electrons in Pb, inducing spin splitting of the Kondo resonance. The spin-polarized nature of the split Kondo resonance and a spin filter effect induced by spin-flip inelastic electron tunneling are revealed by spin-polarized scanning tunneling microscopy and spectroscopy.
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2D ferroelectrics have received wide interest due to the remarkable quantum states of emerging physics at reduced dimensionality, associated with their exotic properties in high-performance and nonvolatile functional devices. Here, by combing molecular beam epitaxy synthesis and scanning tunneling microscopy characterization, two metastable phases of layered In2 Se3 films: ß'- and ß*-In2 Se3 are reported, which develop different types of in-plane spontaneous polarizations, thus resulting in different striped morphologies. The anti-ferroelectric order in ß'-In2 Se3 and ferroelectric order of ß*-In2 Se3 are identified, respectively, down to the 2D limit by comprehensive investigations of structural and spectroscopic signatures, including the lattice distortion, the spatial profile of images, the formation of domain structure, and the electronic band-bending by polarization charges at edges. The ferroelectric switching between those two phases are further controlled via applying an electric field generated from the scanning tunneling microscopy tip in a reversible manner. The intriguing tunability between the (anti-)ferroelectric orders in the 2D limit provides a promising platform for studying the interplay between electronic structure and ferroelectricity in van der Waals materials, and promotes potential development of miniaturized transistors and memory devices based on electric polarizations.
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The fabrication of planar heterojunctions with magnetic van der Waals ultrathin crystals is essential for constructing miniaturized spintronic devices but is yet to be realized. Here, we report the growth of CrTe3 and CrTe2 ultrathin films with molecular beam epitaxy and characterize their morphological and electronic structure through low-temperature scanning tunneling microscopy/spectroscopy. The former is identified as a Mott insulator, and the latter has shown a robust magnetic order previously. Through vacuum annealing, CrTe3 can be transformed into CrTe2, whose relative ratio is controlled via the annealing time. This renders the feasibility of constructing CrTe3-CrTe2 planar heterojunctions, which express atomically sharp interfaces and smooth band bending. We also identified a superstructure conceivably formed via hybrid units of CrTe3 and CrTe2, whose electronic structure exhibits stunning tunability with the length of the superstructure. Our study sets a foundation for the development of magnetic tunneling junctions for building spintronic circuits and engineering electronic states in artificial superlattice structures.
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Studies of single-spin objects are essential for designing emergent quantum states. We investigate a molecular magnet Tb2Pc3 interacting with a superconducting Pb(111) substrate, which hosts unprecedented Yu-Shiba-Rusinov (YSR) subgap states, dubbed spin-orbital YSR states. Upon adsorption of the molecule on Pb, the degeneracy of its lowest unoccupied molecular orbitals (LUMO) is lifted, and the lower LUMO forms a radical spin via charge transfer. This leads to Kondo screening and subgap states. Intriguingly, the YSR states display two pairs of resonances with clearly distinct behavior. The energy of the inner pair exhibits prominent inter and intra molecular variation, and it strongly depends on the tip height. The outer pair, however, shifts only slightly. As is unveiled through theoretical calculations, the two pairs of YSR states originate from the ligand spin and charge-fluctuating higher LUMO, coexisting in a single molecule, but only weakly coupled presumably due to different spatial distribution. Our work paves the way for understanding complex many-body excitations and constructing molecule-based topological superconductivity.
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Optimizing the intrinsic activity of active sites is an appealing strategy for accelerating the kinetics of the catalytic process. Here, a design principle, namely "dual self-built gating", is proposed to tailor the electronic structures of catalysts. Catalytic improvement is confirmed in a model catalyst with a ReS2 -WS2 /WS2 hybridized heterostructure. As demonstrated in experimental and theoretical results, the dual gating can bidirectionally guide electron transfer and redistribute at the interface, endowing the model catalyst with an electron-rich region. The tailored electronic structures balance the adsorption of intermediates and the desorption of hydrogen synergistically to enhance the reaction kinetics for the hydrogen evolution reaction. Interestingly, the effect of dual gating can be easily amplified by the electric field. The overpotential and Tafel slope (49 mV, 35 mV dec-1 ) obtained under the electric field for ReS2 -WS2 /WS2 catalyst with the dual self-built gating effect are far below than those (210 mV, 116 mV dec-1 ) of the pure WS2 catalyst, which exhibits nearly four times improvement. The concept of dual gating can be applied to more systems, offering a new guideline for designing advanced electrocatalysts.
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Intrinsic antiferromagnetism in van der Waals (vdW) monolayer (ML) crystals enriches our understanding of two-dimensional (2D) magnetic orders and presents several advantages over ferromagnetism in spintronic applications. However, studies of 2D intrinsic antiferromagnetism are sparse, owing to the lack of net magnetisation. Here, by combining spin-polarised scanning tunnelling microscopy and first-principles calculations, we investigate the magnetism of vdW ML CrTe2, which has been successfully grown through molecular-beam epitaxy. We observe a stable antiferromagnetic (AFM) order at the atomic scale in the ML crystal, whose bulk is ferromagnetic, and correlate its imaged zigzag spin texture with the atomic lattice structure. The AFM order exhibits an intriguing noncollinear spin reorientation under magnetic fields, consistent with its calculated moderate magnetic anisotropy. The findings of this study demonstrate the intricacy of 2D vdW magnetic materials and pave the way for their in-depth analysis.
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Atomically thin indium selenide (InSe) is a representative two-dimensional (2D) family that have recently attracted extensive interest for their intriguing emerging physics and potential optoelectronic applications with high-performance. Here, by utilizing molecular beam epitaxy and scanning tunneling microscopy, we report a controlled synthesis of InSe thin films down to the monolayer limit and characterization of their electronic properties at atomic scale. Highly versatile growth conditions are developed to fabricate well crystalline InSe films, with a reversible and controllable phase transformation between InSe and In2Se3. The band gap size of InSe films, as enhanced by quantum confinement, increases with decreasing film thickness. Near various categories of lattice imperfections, the band gap becomes significantly enlarged, resulting in a type-I band alignments for lateral heterojunctions. Such band gap enhancement, as unveiled from our first-principles calculations, is ascribed to the local compressive strain imposed by the lattice imperfections. Moreover, InSe films host highly conductive 2D electron gas, manifesting prominent quasiparticle scattering signatures. The 2D electron gas is self-formed via substrate doping of electrons, which shift the Fermi level above the confinement-quantized conduction band. Our study identifies InSe ultrathin film as an appealing system for both fundamental research and potential applications in nanoelectrics and optoelectronics.