In conventional electrides, excess electrons are localized in crystal voids to serve as anions. Most of these electrides are metallic and the metal cations are primarily from the s-block, d-block, or rare-earth elements. Here, we report a class of p-block metal-based electrides found in bilayer SnO and PbO, which are semiconducting and feature electride states in both the valence band (VB) and conduction band (CB), as referred to 2D “bipolar” electrides. These bilayers are hybrid electrides where excess electrons are localized in the interlayer region and hybridize with the orbitals of Sn atoms in the VB, exhibiting strong covalent-like interactions with neighboring metal atoms. Compared to previously studied hybrid electrides, the higher electronegativity of Sn and Pb enhances these covalent-like interactions, leading to largely enhanced semiconducting bandgap of up to 2.5 eV. Moreover, the CBM primarily arises from the overlap between metal states and interstitial charges, denoting a potential electride and forming a free-electron-like (FEL) state with small effective mass. This state offers high carrier mobilities for both electron and hole in bilayer SnO, suggesting its potential as a promising p-type semiconductor material.
Charge carrier densities in electronic heterostructures are typically responsive to external electric fields or chemical doping but rarely to their magnetization history. Here, we demonstrate that magnetization acts as a non-volatile control parameter for the density of states in bilayer graphene (BLG) interfaced with the antiferromagnetic insulator chromium oxychloride (COC). Using capacitance measurements, we observe a hysteretic behavior in the density of states of BLG on a COC substrate in response to an external magnetic field, which is unrelated to the history of electrostatic gating. First-principles calculations revealed that such hysteresis arises from the magnetic-field-controlled charge transfer between BLG and COC during the antiferromagnetic (AFM) to ferrimagnetic-like (FiM) state phase transition of COC. Our work demonstrates that interfacial charging states can be effectively controlled magnetically, and it also shows that capacitance measurement is a suitable technique for detecting subtle changes not detectable via conventional resistivity measurements. These findings broaden the scope of proximity effects and open new possibilities for nanoelectronics applications.
The quantum anomalous Hall (QAH) effect in two-dimensional (2D) topological materials has attracted widespread attention due to its potential for dissipationless chiral edge transport without an external magnetic field, which is highly promising for low-power electronic applications. However, identifying materials that exhibit these properties remains particularly challenging, as only a limited number of such materials are known, raising the intriguing question of whether it is possible to induce the QAH effect in materials with ordinary properties through structural modifications. In this work, we grow an unreported 2D titanium selenide (Ti3Se4) on a Cu(111) substrate using molecular beam epitaxy. Low-energy electron diffraction and scanning tunneling microscopy characterizations reveal a brick-like structure. First-principles calculations and X-ray photoelectron spectroscopy measurements confirm its composition to be Ti3Se4. Our calculations further demonstrate that monolayer Ti3Se4, in its grown form on Cu(111), has the potential to host the QAH effect. Interestingly, when we examine its freestanding form, the monolayer transitions from a QAH insulator candidate into a conventional semiconductor, despite only minor differences in their atomic structures. This transition enlightens us that subtle lattice adjustments can induce a transition from semiconductor to QAH properties in freestanding Ti3Se4. This discovery provides a potential route to engineering practical materials that may exhibit the QAH effect.
The generation of pseudo-magnetic fields in strained graphene leads to quantized Landau levels in the absence of an external magnetic field, providing the potential to achieve a zero-magnetic-field analogue of quantum Hall effect. Here, we report the realization of pseudo-magnetic field in epitaxial graphene by building monolayer CrCl2/graphene heterointerface. The CrCl2 crystal structure exhibits spontaneous breaking of three-fold rotational symmetry, yielding anisotropic displacement field at the interface. Using scanning tunneling spectroscopy, we have discovered a sequence of pseudo-Landau levels associated with massless Dirac fermions. A control experiment performed on CrCl2/NbSe2 interface confirms the origin as the pseudo-magnetic field in the graphene layer that strongly interacts with the CrCl2. More interestingly, the strength of the pseudo-magnetic fields can be tuned by the twist angle between the monolayer CrCl2 and graphene, with a variation of up to threefold, depending on the twist angle of 0° to 30°. This work presents a rare 2D heterojunction for exploring PMF-related physics, such as valley Hall effect, with the advantage of easy and flexible implementation.
Scanning tunneling microscopy (STM) vibronic spectroscopy, which has provided submolecular insights into electron-vibration (vibronic) coupling, faces challenges when probing the pivotal low-frequency vibronic excitations. Because of eigenstate broadening on solid substrates, resolving low-frequency vibronic states demands strong decoupling. This work designs a type II band alignment in STM junction to achieve effective charge-transfer state decoupling. This strategy enables the successful identification of the lowest-frequency Hg(ω1) (Raman-active Hg mode) vibronic excitation within single C60 molecules, which, despite being notably pronounced in electron transport of C60 single-molecule transistors, has remained hidden at submolecular level. Our results show that the observed Hg(ω1) excitation is “anchored” to all molecules, irrespective of local geometry, challenging common understanding of structural definition of vibronic excitation governed by Franck-Condon principle. Density functional theory calculations reveal existence of molecule-substrate interfacial charge-transfer dipole, which, although overlooked previously, drives the dominant Hg(ω1) excitation. This charge-transfer dipole is not specific but must be general at interfaces, influencing vibronic coupling in charge transport.
Individual superatoms were assembled into more complicated nanostructures for diversify their physical properties. Magnetism of assembled superatoms remains, however, ambiguous, particularly in terms of its distance dependence. Here, we report density functional theory calculations on the distance-dependent magnetism of transition metal embedded Au6Te8Se12 (ATS) superatomic dimers. Among the four considered transition metals, which include V, Cr, Mn and Fe, the Cr-embedded Au6Te12Se8 (Cr@ATS) is identified as the most suitable for exploring the inter-superatomic distance-dependent magnetism. We thus focused on Cr@ATS superatomic dimers and found an inter-superatomic magnetization-distance oscillation where three transitions occur for magnetic ordering and/or anisotropy at different inter-superatomic distances. As the inter-superatomic distance elongates, a ferromagnetism (FM)-to-antiferromagnetic (AFM) transition and a sequential AFM-to-FM transition occur, ascribed to competitions among Pauli repulsion and kinetic-energy-gains in formed inter-superatomic Cr-Au-Au-Cr covalent bonds and Te-Te quasi-covalent bonds. For the third transition, in-plane electronic hybridization contributes to the stabilization of the AFM configuration. This work unveils two mechanisms for tuning magnetism through non-covalent interactions and provides a strategy for manipulating magnetism in superatomic assemblies.
