Atomic-Scale Visualization of Multiferroicity in Monolayer NiI2.

Progress in layered van der Waals materials has resulted in the discovery of ferromagnetic and ferroelectric materials down to the monolayer limit. Recently, evidence of the first purely 2D multiferroic material was reported in monolayer NiI2. However, probing multiferroicity with scattering-based and optical bulk techniques is challenging on 2D materials, and experiments on the atomic scale are needed to fully characterize the multiferroic order at the monolayer limit. Here, scanning tunneling microscopy (STM) supported by density functional theory (DFT) calculations is used to probe and characterize the multiferroic order in monolayer NiI2. It is demonstrated that the type-II multiferroic order displayed by NiI2, arising from the combination of a magnetic spin spiral order and a strong spin-orbit coupling, allows probing the multiferroic order in the STM experiments. Moreover, the magnetoelectric coupling of NiI2 is directly probed by external electric field manipulation of the multiferroic domains. The findings establish a novel point of view to analyze magnetoelectric effects at the microscopic level, paving the way toward engineering new multiferroic orders in van der Waals materials and their heterostructures.

Real-Space Imaging of Triplon Excitations in Engineered Quantum Magnets.

Quantum magnets provide a powerful platform to explore complex quantum many-body phenomena. One example is triplon excitations, exotic many-body modes emerging from propagating singlet-triplet transitions. We engineer a minimal quantum magnet from organic molecules and demonstrate the emergence of dispersive triplon modes in one- and two-dimensional assemblies probed with scanning tunneling microscopy and spectroscopy. Our results provide the first demonstration of dispersive triplon excitations from a real-space measurement.

Evidence of Nodal Superconductivity in Monolayer 1H-TaS2 with Hidden Order Fluctuations.

Unconventional superconductors represent one of the fundamental directions in modern quantum materials research. In particular, nodal superconductors are known to appear naturally in strongly correlated systems, including cuprate superconductors and heavy-fermion systems. Van der Waals materials hosting superconducting states are well known, yet nodal monolayer van der Waals superconductors have remained elusive. Here, using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) experiments, it is shown that pristine monolayer 1H-TaS2 realizes a nodal superconducting state. Non-magnetic disorder drives the nodal superconducting state to a conventional gapped s-wave state. Furthermore, many-body excitations emerge close to the gap edge, signalling a potential unconventional pairing mechanism. The results demonstrate the emergence of nodal superconductivity in a van der Waals monolayer, providing a building block for van der Waals heterostructures exploiting unconventional superconducting states.

Visualization of Moiré Magnons in Monolayer Ferromagnet.

Two-dimensional magnetic materials provide an ideal platform to explore collective many-body excitations associated with spin fluctuations. In particular, it should be feasible to explore, manipulate, and ultimately design magnonic excitations in two-dimensional van der Waals magnets in a controllable way. Here we demonstrate the emergence of moiré magnon excitations, stemming from the interplay of spin-excitations in monolayer CrBr3 and the moiré pattern arising from the lattice mismatch with the underlying substrate. The existence of moiré magnons is further confirmed via inelastic quasiparticle interference, showing the appearance of a dispersion pattern correlated with the moiré length scale. Our results provide a direct visualization in real-space of the dispersion of moiré magnons, demonstrating the versatility of moiré patterns in creating emergent many-body excitations.

Control of Molecular Orbital Ordering Using a van der Waals Monolayer Ferroelectric.

2D ferroelectric materials provide a promising platform for the electrical control of quantum states. In particular, due to their 2D nature, they are suitable for influencing the quantum states of deposited molecules via the proximity effect. Here, electrically controllable molecular states in phthalocyanine molecules adsorbed on monolayer ferroelectric material SnTe are reported. The strain and ferroelectric order in SnTe are found to create a transition between two distinct orbital orders in the adsorbed phthalocyanine molecules. By controlling the polarization of the ferroelectric domain using scanning tunneling microscopy (STM), it is successfully demonstrated that orbital order can be manipulated electrically. The results show how ferroelastic coupling in 2D systems allows for control of molecular states, providing a starting point for ferroelectrically switchable molecular orbital ordering and ultimately, electrical control of molecular magnetism.

Confinement-Engineered Superconductor to Correlated-Insulator Transition in a van der Waals Monolayer.

Transition metal dichalcogenides (TMDC) are a rich family of two-dimensional materials displaying a multitude of different quantum ground states. In particular, d3 TMDCs are paradigmatic materials hosting a variety of symmetry broken states, including charge density waves, superconductivity, and magnetism. Among this family, NbSe2 is one of the best-studied superconducting materials down to the monolayer limit. Despite its superconducting nature, a variety of results point toward strong electronic repulsions in NbSe2. Here, we control the strength of the interactions experimentally via quantum confinement and use low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) to demonstrate that NbSe2 is in close proximity to a correlated insulating state. This reveals the coexistence of competing interactions in NbSe2, creating a transition from a superconducting to an insulating quantum correlated state by confinement-controlled interactions. Our results demonstrate the dramatic role of interactions in NbSe2, establishing NbSe2 as a correlated superconductor with competing interactions.

Moiré-Enabled Topological Superconductivity.

The search for artificial topological superconductivity has been limited by the stringent conditions required for its emergence. As exemplified by the recent discoveries of various correlated electronic states in twisted van der Waals materials, moiré patterns can act as a powerful knob to create artificial electronic structures. Here, we demonstrate that a moiré pattern between a van der Waals superconductor and a monolayer ferromagnet creates a periodic potential modulation that enables the realization of a topological superconducting state that would not be accessible in the absence of the moiré. The magnetic moiré pattern gives rise to Yu-Shiba-Rusinov minibands and periodic modulation of the Majorana edge modes that we detect using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). Moiré patterns and, more broadly, periodic potential modulations are powerful tools to overcome the conventional constraints for realizing and controlling topological superconductivity.

Two-Dimensional Metal-Organic Framework on Superconducting NbSe2.

The combination of two-dimensional (2D) materials into vertical heterostructures has emerged as a promising path to designer quantum materials with exotic properties. Here, we extend this concept from inorganic 2D materials to 2D metal-organic frameworks (MOFs) that offer additional flexibility in realizing designer heterostructures. We successfully fabricate a monolayer 2D Cu-dicyanoanthracene MOF on a 2D van der Waals NbSe2 superconducting substrate. The structural and electronic properties of two different phases of the 2D MOF are characterized by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS), complemented by density-functional theory (DFT) calculations. These experiments allow us to follow the formation of the kagome band structure from Star of David-shaped building blocks. This work extends the synthesis and electronic tunability of 2D MOFs beyond the electronically less relevant metal and semiconducting surfaces to superconducting substrates, which are needed for the development of emerging quantum materials such as topological superconductors.

Artificial heavy fermions in a van der Waals heterostructure.

Heavy-fermion systems represent one of the paradigmatic strongly correlated states of matter1-5. They have been used as a platform for investigating exotic behaviour ranging from quantum criticality and non-Fermi liquid behaviour to unconventional topological superconductivity4-12. The heavy-fermion phenomenon arises from the exchange interaction between localized magnetic moments and conduction electrons leading to Kondo lattice physics, and represents one of the long-standing open problems in quantum materials3. In a Kondo lattice, the exchange interaction gives rise to a band with heavy effective mass. This intriguing phenomenology has so far been realized only in compounds containing rare-earth elements with 4f or 5f electrons1,4,13,14. Here we realize a designer van der Waals heterostructure where artificial heavy fermions emerge from the Kondo coupling between a lattice of localized magnetic moments and itinerant electrons in a 1T/1H-TaS2 heterostructure. We study the heterostructure using scanning tunnelling microscopy and spectroscopy and show that depending on the stacking order of the monolayers, we can reveal either the localized magnetic moments and the associated Kondo effect, or the conduction electrons with a heavy-fermion hybridization gap. Our experiments realize an ultimately tunable platform for future experiments probing enhanced many-body correlations, dimensional tuning of quantum criticality and unconventional superconductivity in two-dimensional artificial heavy-fermion systems15-17.

Synthesis and Properties of Monolayer MnSe with Unusual Atomic Structure and Antiferromagnetic Ordering.

Transition metal chalcogenides (TMCs) are a large family of 2D materials that are currently attracting intense interest. TMCs with 3d transition metals provide opportunities for introducing magnetism and strong correlations into the material with manganese standing out as a particularly attractive option due to its large magnetic moment. Here we report on the successful synthesis of monolayer manganese selenide on a NbSe2 substrate. Using scanning tunneling microscopy and spectroscopy experiments and global structure prediction calculations at the density functional theory level, we identify the atomic structure and magnetic and electronic properties of the layered Mn2Se2 phase. The structure is similar to the layered bulk phase of CuI or a buckled bilayer of h-BN. Interestingly, our results suggest that the monolayer is antiferromagnetic, but with an unusual out-of-plane ordering that results in two ferromagnetic planes.

Electronic Characterization of a Charge-Transfer Complex Monolayer on Graphene.

Organic charge-transfer complexes (CTCs) formed by strong electron acceptor and strong electron donor molecules are known to exhibit exotic effects such as superconductivity and charge density waves. We present a low-temperature scanning tunneling microscopy and spectroscopy (LT-STM/STS) study of a two-dimensional (2D) monolayer CTC of tetrathiafulvalene (TTF) and fluorinated tetracyanoquinodimethane (F4TCNQ), self-assembled on the surface of oxygen-intercalated epitaxial graphene on Ir(111) (G/O/Ir(111)). We confirm the formation of the charge-transfer complex by dI/dV spectroscopy and direct imaging of the singly occupied molecular orbitals. High-resolution spectroscopy reveals a gap at zero bias, suggesting the formation of a correlated ground state at low temperatures. These results point to the possibility to realize and study correlated ground states in charge-transfer complex monolayers on weakly interacting surfaces.

Electronic and Magnetic Characterization of Epitaxial CrBr3 Monolayers on a Superconducting Substrate.

The ability to imprint a given material property to another through a proximity effect in layered 2D materials has opened the way to the creation of designer materials. Here, molecular-beam epitaxy is used for direct synthesis of a superconductor-ferromagnet heterostructure by combining superconducting niobium diselenide (NbSe2 ) with the monolayer ferromagnetic chromium tribromide (CrBr3 ). Using different characterization techniques and density-functional theory calculations, it is confirmed that the CrBr3 monolayer retains its ferromagnetic ordering with a magnetocrystalline anisotropy favoring an out-of-plane spin orientation. Low-temperature scanning tunneling microscopy measurements show a slight reduction of the superconducting gap of NbSe2 and the formation of a vortex lattice on the CrBr3 layer in experiments under an external magnetic field. The results contribute to the broader framework of exploiting proximity effects to realize novel phenomena in 2D heterostructures.

Topological superconductivity in a van der Waals heterostructure.

Exotic states such as topological insulators, superconductors and quantum spin liquids are often challenging or impossible to create in a single material1-3. For example, it is unclear whether topological superconductivity, which has been suggested to be a key ingredient for topological quantum computing, exists in any naturally occurring material4-9. The problem can be circumvented by deliberately selecting the combination of materials in heterostructures so that the desired physics emerges from interactions between the different components1,10-15. Here we use this designer approach to fabricate van der Waals heterostructures that combine a two-dimensional (2D) ferromagnet with a superconductor, and we observe 2D topological superconductivity in the system. We use molecular-beam epitaxy to grow 2D islands of ferromagnetic chromium tribromide16 on superconducting niobium diselenide. We then use low-temperature scanning tunnelling microscopy and spectroscopy to reveal the signatures of one-dimensional Majorana edge modes. The fabricated 2D van der Waals heterostructure provides a high-quality, tunable system that can be readily integrated into device structures that use topological superconductivity. The layered heterostructures can be readily accessed by various external stimuli, potentially allowing external control of 2D topological superconductivity through electrical17, mechanical18, chemical19 or optical means20.

Publisher Correction: Topological frustration induces unconventional magnetism in a nanographene.

An amendment to this paper has been published and can be accessed via a link at the top of the paper.

Topological frustration induces unconventional magnetism in a nanographene.

The chemical versatility of carbon imparts manifold properties to organic compounds, where magnetism remains one of the most desirable but elusive1. Polycyclic aromatic hydrocarbons, also referred to as nanographenes, show a critical dependence of electronic structure on the topologies of the edges and the π-electron network, which makes them model systems with which to engineer unconventional properties including magnetism. In 1972, Erich Clar envisioned a bow-tie-shaped nanographene, C38H18 (refs. 2,3), where topological frustration in the π-electron network renders it impossible to assign a classical Kekulé structure without leaving unpaired electrons, driving the system into a magnetically non-trivial ground state4. Here, we report the experimental realization and in-depth characterization of this emblematic nanographene, known as Clar's goblet. Scanning tunnelling microscopy and spin excitation spectroscopy of individual molecules on a gold surface reveal a robust antiferromagnetic order with an exchange-coupling strength of 23 meV, exceeding the Landauer limit of minimum energy dissipation at room temperature5. Through atomic manipulation, we realize switching of magnetic ground states in molecules with quenched spins. Our results provide direct evidence of carbon magnetism in a hitherto unrealized class of nanographenes6, and prove a long-predicted paradigm where topological frustration entails unconventional magnetism, with implications for room-temperature carbon-based spintronics7,8.

Observation of Coexistence of Yu-Shiba-Rusinov States and Spin-Flip Excitations.

We investigate the spectral evolution in different metal phthalocyanine molecules on NbSe2 surface using scanning tunnelling microscopy (STM) as a function of the coupling with the substrate. For manganese phthalocyanine (MnPc), we demonstrate a smooth spectral crossover from Yu-Shiba-Rusinov (YSR) bound states to spin-flip excitations. This has not been observed previously and it is in contrast to simple theoretical expectations. We corroborate the experimental findings using numerical renormalization group calculations. Our results provide fundamental new insight on the behavior of atomic scale magnetic/SC hybrid systems, which is important, for example, for engineered topological superconductors and spin logic devices.

Coupled Yu-Shiba-Rusinov States in Molecular Dimers on NbSe2.

Magnetic impurities have a dramatic effect on superconductivity by breaking the time-reversal symmetry and inducing so-called Yu-Shiba-Rusinov (YSR) low energy bound states within the superconducting gap. The spatial extent of YSR states is greatly enhanced in two-dimensional (2D) systems, which should facilitate the formation of coupled states. Here, we observe YSR states on single cobalt phthalocyanine (CoPC) molecules on a 2D superconductor NbSe2 using low-temperature scanning tunneling microscopy (STM) and spectroscopy. We use STM lateral manipulation to create controlled CoPc dimers and demonstrate the formation of coupled YSR states. The experimental results are corroborated by theoretical analysis of the coupled states in lattice and continuum models.

Synthesis of Extended Atomically Perfect Zigzag Graphene - Boron Nitride Interfaces.

The combination of several materials into heterostructures is a powerful method for controlling material properties. The integration of graphene (G) with hexagonal boron nitride (BN) in particular has been heralded as a way to engineer the graphene band structure and implement spin- and valleytronics in 2D materials. Despite recent efforts, fabrication methods for well-defined G-BN structures on a large scale are still lacking. We report on a new method for producing atomically well-defined G-BN structures on an unprecedented length scale by exploiting the interaction of G and BN edges with a Ni(111) surface as well as each other.

Hierarchy of Chemical Bonding in the Synthesis of Fe-Phthalocyanine on Metal Surfaces: A Local Spectroscopy Approach.

Scanning tunneling spectroscopy (STS) has become a key tool for accessing properties of organometallic molecules adsorbed on surfaces. However, the rich variety of signatures makes it sometimes a difficult task to find out which feature is intrinsic to the molecule, i.e., relevant for a metal-ligand interaction or related to the interaction of the molecule with the substrate. Here we study the prototype covalent self-assembly of FePc and probe how electronic/magnetic properties at the local scale change as a function of temperature-induced step-by-step assembly, starting from TCNB (1,2,4,5- Tetracyanobenzene) molecular and Fe atomic precursors. Intermediate complexes with tetra-coordinated Fe atoms are then used both, as synthons for the FePc and as identifiers of specific features of the STS. As observed by STS and confirmed by spin-polarized DFT calculations, the occupied dπ states of Fe are present in both the FePc and Fe(TCNB)2 on Au(111). The main difference appears in the dz(2) states, which play a key role in magnetism as confirmed by the presence/absence of the Kondo resonance. A comprehensive picture is obtained by following with STS the hybridization of the dz(2) orbital of Fe to various substrates (Cu, Au and Co). Finally it is demonstrated that FePc units can be created by on-surface polymerization from the Fe(TCNB)2 network upon thermal annealing.