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Carbohydrates, essential biological building blocks, exhibit functional mechanisms tied to their intricate stereochemistry. Subtle stereochemical differences, such as those between the anomers maltose and cellobiose, lead to distinct properties due to their differing glycosidic bonds; the former is digestible by humans, while the latter is not. This underscores the importance of precise structural determination of individual carbohydrate molecules for deeper functional insights. However, their structural complexity and conformational flexibility, combined with the high spatial resolution needed, have hindered direct imaging of carbohydrate stereochemistry. Here, we employ non-contact atomic force microscopy integrated with a data-efficient, multi-fidelity structure search approach accelerated by machine learning integration to determine the precise 3D atomic coordinates of two carbohydrate anomers. We observe that glycosidic bond stereochemistry regulates on-surface chiral selection in carbohydrate self-assemblies. The reconstructed models, validated against experimental data, provide reliable atomic-scale structural evidence, uncovering the origin of on-surface chirality from carbohydrate anomerism. Our study confirms that nc-AFM is a reliable technique for real-space discrimination of carbohydrate stereochemistry at the single-molecule level, providing a pathway for bottom-up investigations into the structure-property relationships of carbohydrates in biological research and materials science.

Topological crystalline insulators (TCIs) host topological phases of matter protected by crystal symmetries. Topological surface states in three-dimensional TCIs have been predicted and observed in IV-VI SnTe-class semiconductors. Despite the prediction of a two-dimensional (2D) TCI characterized by two pairs of edge states inside the bulk gap, materials challenges have thus far prevented its experimental realization. Here we report the growth and characterization of bilayer SnTe on the 2$H$-NbSe$_2$ substrate by molecular beam epitaxy and scanning tunneling microscopy. We experimentally observe two anticorrelated, periodically modulated pairs of conducting edge states along the perimeters of the sample with a large band gap exceeding $0.2$ eV. We identify these states with a 2D TCI through first principles calculations. Finally, we probe the coupling of adjacent topological edge states and demonstrate the resulting energy shift driven by a combination of electrostatic interactions and tunneling coupling. Our work opens the door to investigations of tunable topological states in 2D TCIs, of potential impact for spintronics and nanoelectronics applications at room temperature.

Scanning Probe Microscopy (SPM) techniques have shown great potential in fabricating nanoscale structures endowed with exotic quantum properties achieved through various manipulations of atoms and molecules. However, the selection of proper manipulation parameters requires extensive domain knowledge, which is not necessarily transferable to new systems. Therefore, efficient and autonomous SPM techniques are needed to reduce the reliance on user supervision and learn optimal strategies for new systems, in particular for the challenge of controlling chemical reactions. In this paper, we developed a software infrastructure named AutoOSS (Autonomous On-Surface Synthesis) to automate bromine removal from Zn(II)-5,15- bis(4-bromo-2,6-dimethylphenyl)porphyrin (ZnBr2Me4DPP) on Au(111), using neural network models to interpret STM outputs and deep reinforcement learning models to optimize manipulation parameters. This is further supported by Bayesian Optimization Structure Search (BOSS) and Density Functional Theory (DFT) computations to explore 3D structures and reaction mechanisms based on STM images.

Carbon-based nanostructures possessing {\pi}-electron magnetism have attracted tremendous interest due to their great potential for nano spintronics. In particular, quantum chains with magnetic molecular units synthesized by on-surface reactions provide an ideal playground for investigating magnetic exchange interactions between localized spin components. Here, we present an extensive study of antiferromagnetic nanographene chains with the diazahexabenzocoronene molecule as the repeating unit. A combination of bond-resolved scanning tunneling microscopy, density functional theory and quantum spin models revealed their detailed structures and electronic and magnetic properties. We found that the antiferromagnetic chains host a collective state featuring gapped excitations for an even number of repeating units and one featuring a Kondo excitation for an odd number. Comparing with exact many-body quantum spin models, our molecular chains provide the realization of an entangled quantum Heisenberg model. Coupled with the tunability of the molecular building blocks, these systems can act as an ideal platform for the experimental realization of topological spin lattices.

Van der Waals heterostructures have emerged as an ideal platform for creating engineered artificial electronic states. While vertical heterostructures have been extensively studied, realizing high-quality lateral heterostructures with atomically sharp interfaces remains a major experimental challenge. Here, we advance a one-pot two-step molecular beam lateral epitaxy approach and successfully synthesize atomically well-defined 1T-VSe$_2$ -- 1H-NbSe$_2$ lateral heterostructures. We demonstrate the formation of defect-free lateral heterostructures and characterize their electronic structure using scanning tunnelling microscopy and spectroscopy together with density functional theory calculations. We find additional electronic states at the one-dimensional interface as well as signatures of Kondo resonances in a side-coupled geometry. Our experiments explore the full potential of lateral heterostructures for realizing exotic electronic states in low-dimensional systems for further studies of artificial designer quantum materials.

The doped Hubbard model is one of the paradigmatic platforms to engineer exotic quantum many-body states, including charge-ordered states, strange metals and unconventional superconductors. While undoped and doped correlated phases have been experimentally realized in a variety twisted van der Waals materials, experiments in monolayer materials, and in particular 1T transition metal dichalcogenides, have solely reached the conventional insulating undoped regime. Correlated phases in monolayer two-dimensional materials have much higher associated energy scales than their twisted counterparts, making doped correlated monolayers an attractive platform for high temperature correlated quantum matter. Here, we demonstrate the realization of a doped Mott phase in a van der Waals dichalcogenide 1T-NbSe$_2$ monolayer. The system is electron doped due to electron transfer to a monolayer van der Waals substrate via proximity, leading to a correlated triangular lattice with both half-filled and fully-filled sites. We analyze the distribution of the half-filled and filled sites and show the arrangement is unlikely to be controlled by disorder alone, and we show that the presence of competing non-local many-body correlations would account for the charge correlations found experimentally. Our results establish 1T-NbSe$_2$ as a potential monolayer platform to explore correlated doped Mott physics in a frustrated lattice.

Controlling zero bias anomalies in magnetic atoms provides a promising strategy to engineer tunable quantum many-body excitations. Here we show how two different quantum impurities featuring spinaron and Kondo excitations can be controlled via quantum confinement engineering by using circular quantum corrals on a Ag(111) surface. In corrals built from both Ag and Co adatoms, the width of the zero bias anomaly in the central Co adatom oscillates as a function of corral radius with a period of half of the Ag(111) surface state wavelength. Parameters extracted for Co/Ag(111) show only small differences in extracted spinaron zero-bias anomaly between corral walls built from Ag or Co adatoms. In quantum corrals occupied with metal-free phthalocyanine, a $S=1/2$ Kondo system, we observe notable changes in the zero bias anomaly lineshape as a function of corral radius. Our results offer insight into many-body Kondo and spinaron resonances where the electronic density is controlled by confinement engineering.

The interaction of water with surfaces is crucially important in a wide range of natural and technological settings. In particular, at low temperatures, unveiling the atomistic structure of adsorbed water clusters would provide valuable data for understanding the ice nucleation process. Using high-resolution Atomic Force Microscopy (AFM) and Scanning Tunnelling Microscopy, several studies have demonstrated the presence of water pentamers, hexamers, heptamers (and of their combinations) on a variety of metallic surfaces, as well the initial stages of 2D ice growth on an insulating surface. However, in all these cases, the observed structures were completely flat, providing a relatively straightforward path to interpretation. Here, we present high-resolution AFM measurements of several new water clusters on Au(111) and Cu(111), whose understanding presents significant challenges, due to both their highly 3D configuration and to their large size. For each of them, we use a combination of machine learning, atomistic modelling with neural network potentials and statistical sampling to propose an underlying atomic structure, finally comparing its AFM simulated images to the experimental ones. These results provide new insights into the early phases of ice formation, which is a ubiquitous phenomenon ranging from biology to astrophysics.

The Kondo effect describes the scattering of conduction electrons by magnetic impurities, manifesting as an electronic resonance at the Fermi energy with a distinctive temperature evolution. In this letter, we present a critical evaluation of the current methodology employed to demonstrate Kondo behavior in transport measurements, underscoring the limitations of established theoretical frameworks and the influence of extrinsic broadening. We introduce a novel approach for analyzing spectroscopic indicators of the Kondo effect, employing the Hurwitz-Fano lineshape as a model for the Kondo resonance in the presence of extrinsic broadening. Through precise scanning tunneling spectroscopy measurements on an exemplary spin-1/2 Kondo system, phenalenyl on Au(111), we demonstrate the efficacy of our proposed protocol in extracting accurate intrinsic Kondo linewidths from finite-temperature measurements. The extracted linewidths exhibit a robust fit with a recently derived expression for the temperature-dependent intrinsic Kondo linewidth, providing compelling evidence for the validity of the underlying theory., Comment: 6 pages, 4 figures; plus supplemental material (13 pages, 9 Figures)

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 two-dimensional multiferroic material was reported in monolayer NiI$_2$. 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, we use scanning tunneling microscopy (STM) supported by theoretical calculations based on density functional theory (DFT) to probe and characterize the multiferroic order in monolayer NiI$_2$. We demonstrate that the type-II multiferroic order displayed by NiI$_2$, 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, we directly probe the magnetoelectric coupling of NiI$_2$ by external electric field manipulation of the multiferroic domains. Our findings establish a novel point of view to analyse magnetoelectric effects at the microscopic level, paving the way towards engineering new multiferroic orders in van der Waals materials and their heterostructures.

Designer heterostructures, where the desired physics emerges from the controlled interactions between different components, represent one of the most powerful strategies to realize unconventional electronic states. This approach has been particularly fruitful in combining magnetism and superconductivity to create exotic superconducting states. In this work, we use a heterostructure platform combining supramolecular metal complexes (SMCs) with a quasi-2D van der Waals (vdW) superconductor NbSe$_2$. Our scanning tunneling microscopy (STM) measurements demonstrate the emergence of Yu-Shiba-Rusinov (YSR) bands arising from the interaction between the SMC magnetism and the NbSe$_2$ superconductivity. Using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements, we show the presence of antiferromagnetic coupling between the SMC units. These result in the emergence of an unconventional $3\times3$ reconstruction in the magnetic ground state that is directly reflected in real space modulation of the YSR bands. The combination of flexible molecular building blocks, frustrated magnetic textures, and superconductivity in heterostructures establishes a fertile starting point to fabricating tunable quantum materials, including unconventional superconductors and quantum spin liquids.

Quantum magnets provide a powerful platform to explore complex quantum many-body phenomena. One example is triplon excitations, exotic many-body modes emerging from deconfined singlet-triplet transitions with no single particle analog. Triplons are challenging to observe in conventional materials, as the energy scales of singlet-triplet transitions are associated with Hund's energy and are dramatically larger than the typical bandwidth of spin fluctuations. 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. We show the variable bandwidth of triplon excitations in these two different geometries. Our results provide the first demonstration of dispersive triplon excitations from a real-space measurement, suggesting their potential engineering to realize exotic many-body phenomena in quantum magnets without breaking time-reversal symmetry.

The existence of water dimers in equilibrium water vapor at room temperature and their anomalous properties revealed by recent studies suggest the benchmark role of water dimer in both experiment and theory. However, there has been a limited observation of individual water dimers due to the challenge of water separation and generation at the single-molecule level. Here, we achieve real-space imaging of individual confined water dimers embedded inside self-assembled layer of a DNA base, adenine, on Ag(111). The hydration of the adenine layers by these water dimers causes a local surface chiral inversion in a way that the neighboring homochiral adenine molecules become heterochiral after hydration, resulting in a mismatched hydrogen-bond pattern between neighboring adenine molecules. Furthermore, the mutual influence between the adenine superstructure and these dynamic confined water dimers is corroborated by theoretical simulation and calculations. The observation of single confined water dimers offers an unprecedented approach to studying the fundamental forms of water clusters and their interaction with the local chemical environment., Comment: Revision: added a missing inset to Figure 1b

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 moir\'e magnon excitations, stemming from the interplay of spin-excitations in monolayer CrBr$_3$ and the moir\'e pattern stemming from the lattice mismatch with the underlying substrate. The existence of moir\'e magnons is further confirmed via inelastic quasiparticle interference, showing the appearance of a dispersion pattern correlated with the moir\'e length scale. Our results provide a direct visualization in real-space of the dispersion of moir\'e magnons, demonstrating the versatility of moir\'e patterns in creating emerging many-body excitations.

Two-dimensional (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, we report electrically controllable molecular states in phthalocyanine molecules adsorbed on monolayer ferroelectric material SnTe. In particular, we demonstrate that the strain and ferroelectric order in SnTe creates 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), we have successfully demonstrated that orbital order can be manipulated electrically. Our results show how ferroelastic coupling in 2D systems allows control of molecular states, providing a starting point for ferroelectrically switchable molecular orbital ordering and ultimately, electrical control of molecular magnetism.

Atomic-scale manipulation in scanning tunneling microscopy has enabled the creation of quantum states of matter based on artificial structures and extreme miniaturization of computational circuitry based on individual atoms. The ability to autonomously arrange atomic structures with precision will enable the scaling up of nanoscale fabrication and expand the range of artificial structures hosting exotic quantum states. However, the \textit{a priori} unknown manipulation parameters, the possibility of spontaneous tip apex changes, and the difficulty of modeling tip-atom interactions make it challenging to select manipulation parameters that can achieve atomic precision throughout extended operations. Here we use deep reinforcement learning (DRL) to control the real-world atom manipulation process. Several state-of-the-art reinforcement learning techniques are used jointly to boost data efficiency. The reinforcement learning agent learns to manipulate Ag adatoms on Ag(111) surfaces with optimal precision and is integrated with path planning algorithms to complete an autonomous atomic assembly system. The results demonstrate that state-of-the-art deep reinforcement learning can offer effective solutions to real-world challenges in nanofabrication and powerful approaches to increasingly complex scientific experiments at the atomic scale.

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, we show that pristine monolayer 1H-TaS$_2$ realizes a nodal superconducting state. By including non-magnetic disorder, we drive the nodal superconducting state to a conventional gapped s-wave state. Furthermore, we observe the emergence of many-body excitations close to the gap edge, signalling a potential unconventional pairing mechanism. Our 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.

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 NbSe$_2$ 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 bandstructure from Star of David -shaped building blocks. This work extends the synthesis and electronic tuneability 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.

While offering unprecedented resolution of atomic and electronic structure, Scanning Probe Microscopy techniques have found greater challenges in providing reliable electrostatic characterization at the same scale. In this work, we introduce Electrostatic Discovery Atomic Force Microscopy, a machine learning based method which provides immediate quantitative maps of the electrostatic potential directly from Atomic Force Microscopy images with functionalized tips. We apply this to characterize the electrostatic properties of a variety of molecular systems and compare directly to reference simulations, demonstrating good agreement. This approach opens the door to reliable atomic scale electrostatic maps on any system with minimal computational overhead.

The advent of on-surface chemistry under vacuum has vastly increased our capabilities to synthesize carbon-nanomaterials with atomic precision. Among the types of target structures that have been synthesized by these means, graphene nanoribbons (GNRs) have probably attracted the most attention. In this context, the vast majority of GNRs have been synthesized from the same chemical reaction: Ullmann coupling followed by cyclodehydrogenation. Here, we provide a detailed study of the growth process of 5-atom-wide armchair GNRs starting from dibromoperylene. Combining scanning probe microscopy with temperature-dependent XPS measurements and theoretical calculations, we show that the GNR growth departs from the conventional reaction scenario. Instead, precursor molecules couple by means of a concerted mechanism whereby two covalent bonds are formed simultaneously, along with a concomitant dehydrogenation. Indeed, this novel reaction path is responsible for the straight GNR growth, something remarkable considering the initial mixture of reactant isomers with irregular metal-organic intermediates that we find. The provided insight will not only help understanding the reaction mechanisms of other reactants, but also serve as a guide for the design of new precursor molecules.

Controlling the properties of organic/inorganic materials requires detailed knowledge of their molecular adsorption geometries. This is often unattainable, even with current state-of-the-art tools. Visualizing the structure of complex non-planar adsorbates with atomic force microscopy (AFM) is challenging, and identifying it computationally is intractable with conventional structure search. In this fresh approach, cross-disciplinary tools are integrated for a robust and automated identification of 3D adsorbate configurations. Bayesian optimization is employed with first-principles simulations for accurate and unbiased structure inference of multiple adsorbates. The corresponding AFM simulations then allow fingerprinting adsorbate structures that appear in AFM experimental images. In the instance of bulky (1S)-camphor adsorbed on the Cu(111) surface, three matching AFM image contrasts are found, which allow correlating experimental image features to distinct cases of molecular adsorption., Comment: 9 pages, 4 figures, 1 table

Heavy fermion systems represent one of the paradigmatic strongly correlated states of matter. They have been used as a platform for investigating exotic behavior ranging from quantum criticality and non-Fermi liquid behavior to unconventional topological superconductivity. Heavy fermions arise from the exchange interaction between localized magnetic moments and conduction electrons that leads to the well-known Kondo effect. In a Kondo lattice, the interaction between the localized moments gives rise to a band with heavy effective mass. This intriguing phenomenology has so far only been realized in compounds containing rare-earth elements with 4f or 5f electrons. 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-TaS$_2$ heterostructure. We study the heterostructure using scanning tunneling microscopy (STM) and spectroscopy (STS) and show that depending on the stacking order of the monolayers, we can either reveal the localized magnetic moments and the associated Kondo effect, or the conduction electrons with a heavy-fermion hybridization gap. Our experiments realize an ultimately tuneable platform for future experiments probing enhanced many-body correlations, dimensional tuning of quantum criticality, and unconventional superconductivity in two-dimensional artificial heavy-fermion systems.

Van der Waals materials can be easily combined in lateral and vertical heterostructures, providing an outstanding platform to engineer elusive quantum states of matter. However, a critical problem in material science is to establish tangible links between real materials properties and terms that can be cooked up on the model Hamiltonian level to realize different exotic phenomena. Our review aims to do precisely this: we first discuss, in a way accessible to the materials community, what ingredients need to be included in the hybrid quantum materials recipe, and second, we elaborate on the specific materials that would possess the necessary qualities. We will review the well-established procedures for realizing 2D topological superconductors, quantum spin-liquids and flat bands systems, emphasizing the connection between well-known model Hamiltonians and real compounds. We will use the most recent experimental results to illustrate the power of the designer approach., Comment: 13 pages, 6 figures, review

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., Comment: Manuscript and Supplementary Information, 36 pages

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, moir\'e patterns can act as a powerful knob to create artificial electronic structures. Here, we demonstrate that a moir\'e 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 moir\'e. The magnetic moir\'e 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). Moir\'e patterns and, more broadly, periodic potential modulations are powerful tools to overcome the conventional constrains for realizing and controlling topological superconductivity., Comment: 6 pages, 4 figures

Transition metal dichalcogenides (TMDC) are a rich family of two-dimensional materials displaying a multitude of different quantum ground states. In particular, d$^3$ TMDCs are paradigmatic materials hosting a variety of symmetry broken states, including charge density waves, superconductivity, and magnetism. Among this family, NbSe$_2$ is one of the best-studied superconducting materials down to the monolayer limit. Despite its superconducting nature, a variety of results point towards strong electronic repulsions in NbSe$_2$. 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 NbSe$_2$ is in close proximity to a correlated insulating state. This reveals the coexistence of competing interactions in NbSe$_2$, 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 NbSe$_2$, establishing NbSe$_2$ as a correlated superconductor with competing interactions.

The ability to imprint a given material property to another through proximity effect in layered two-dimensional materials has opened the way to the creation of designer materials. Here, we use molecular-beam epitaxy (MBE) for a direct synthesis of a superconductor-magnet hybrid heterostructure by combining superconducting niobium diselenide (NbSe$_2$) with the monolayer ferromagnetic chromium tribromide (CrBr$_3$). Using different characterization techniques and density-functional theory (DFT) calculations, we have confirmed that the CrBr$_3$ monolayer retains its ferromagnetic ordering with a magnetocrystalline anisotropy favoring an out-of-plane spin orientation. Low-temperature scanning tunneling microscopy (STM) measurements show a slight reduction of the superconducting gap of NbSe$_2$ and the formation of a vortex lattice on the CrBr$_3$ layer in experiments under an external magnetic field. Our results contribute to the broader framework of exploiting proximity effects to realize novel phenomena in 2D heterostructures.

Achieving large-area uniform two-dimensional (2D) metal-organic frameworks (MOFs) and controlling their electronic properties on inert surfaces is a big step towards future applications in electronic devices. Here we successfully fabricated a 2D monolayer Cu-dicyanoanthracene (DCA) MOF with long-range order on an epitaxial graphene surface. Its structural and electronic properties are studied by low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS) complemented by density-functional theory (DFT) calculations. We demonstrate access to multiple molecular charge states in the 2D MOF using tip-induced local electric fields. We expect that a similar strategy could be applied to fabricate and characterize 2D MOFs with exotic, engineered electronic states.

Certain lattices with specific geometries have one or more spectral bands that are strictly flat, i.e. the electron energy is independent of the momentum. This can occur robustly irrespective of the specific couplings between the lattices sites due to the lattice symmetry, or it can result from fine-tuned couplings between the lattice sites. While the theoretical picture behind flat electronic bands is well-developed, experimental realization of these lattices has proven challenging. Utilizing scanning tunnelling microscopy (STM) and spectroscopy (STS), we manipulate individual vacancies in a chlorine monolayer on Cu(100) to construct various atomically precise 1D lattices with engineered flat bands. We realize experimentally both gapped and gapless flat band systems with single or multiple flat bands. We also demonstrate tuneability of the energy of the flat bands and how they can be switched "on" and "off" by breaking and restoring the symmetry of the lattice geometry. The experimental findings are corroborated by tight-binding calculations. Our results constitute the first experimental realizations of engineered flat bands in a 1D solid-state system and pave the way towards the construction of e.g. topological flat band systems and experimental tests of flat-band-assisted superconductivity in a fully controlled system.

The designer approach has become a new paradigm in accessing novel quantum phases of matter. Moreover, the realization of exotic states such as topological insulators, superconductors and quantum spin liquids often poses challenging or even contradictory demands for any single material. For example, it is presently unclear if topological superconductivity, which has been suggested as a key ingredient for topological quantum computing, exists at all in any naturally occurring material . This problem can be circumvented by using designer heterostructures combining different materials, where the desired physics emerges from the engineered interactions between the different components. Here, we employ the designer approach to demonstrate two major breakthroughs - the fabrication of van der Waals (vdW) heterostructures combining 2D ferromagnetism with superconductivity and the observation of 2D topological superconductivity. We use molecular-beam epitaxy (MBE) to grow two-dimensional islands of ferromagnetic chromium tribromide (CrBr$_3$) on superconducting niobium diselenide (NbSe$_2$) and show the signatures of one-dimensional Majorana edge modes using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). The fabricated two-dimensional vdW heterostructure provides a high-quality controllable platform that can be integrated in device structures harnessing topological superconductivity. Finally, layered heterostructures can be readily accessed by a large variety of external stimuli potentially allowing external control of 2D topological superconductivity through electrical, mechanical, chemical, or optical means.

Vertical integration of two-dimensional (2D) van der Waals (vdW) materials with different quantum ground states is predicted to lead to novel electronic properties that are not found in the constituent layers. Here, we present the direct synthesis of superconductor-magnet hybrid heterostructures by combining superconducting niobium diselenide (NbSe$_2$) with the monolayer (ML) vanadium diselenide (VSe$_2$). More significantly, the in-situ growth in ultra-high vacuum (UHV) allows to produce a clean and an atomically sharp interfaces. Combining different characterization techniques and density-functional theory (DFT) calculations, we investigate the electronic and magnetic properties of VSe$_2$ on NbSe$_2$. Low temperature scanning tunneling microscopy (STM) measurements demonstrate a reduction of the superconducting gap on VSe$_2$ layer. This together with the lack of charge density wave signatures indicates magnetization of the sheet, but not of a conventional itinerant ferromagnet.

Atomic force microscopy (AFM) with molecule-functionalized tips has emerged as the primary experimental technique for probing the atomic structure of organic molecules on surfaces. Most experiments have been limited to nearly planar aromatic molecules, due to difficulties with interpretation of highly distorted AFM images originating from non-planar molecules. Here we develop a deep learning infrastructure that matches a set of AFM images with a unique descriptor characterizing the molecular configuration, allowing us to predict the molecular structure directly. We apply this methodology to resolve several distinct adsorption configurations of 1S-camphor on Cu(111) based on low-temperature AFM measurements. This approach will open the door to apply high-resolution AFM to a large variety of systems for which routine atomic and chemical structural resolution on the level of individual objects/molecules would be a major breakthrough.

The fabrication of atomically precise structures with designer electronic properties is one of the emerging topics in condensed matter physics. The required level of structural control can either be reached through atomic manipulation using the tip of a scanning tunneling microscope (STM) or by bottom-up chemical synthesis. In this review, we focus on recent progress in constructing novel, atomically precise artificial materials: artificial lattices built through atom manipulation and graphene nanoribbons (GNRs) realized by on-surface synthesis. We summarize the required theoretical background and the latest experiments on artificial lattices, topological states in one-dimensional lattices, experiments on graphene nanoribbons and graphene nanoribbon heterostructures, and topological states in graphene nanoribbons. Finally, we conclude our review with an outlook to designer quantum materials with engineered electronic structure.

On-surface metal-organic coordination provides a promising way for synthesizing different two-dimensional lattice structures that have been predicted to possess exotic electronic properties. Using scanning tunneling microscopy (STM) and spectroscopy (STS), we studied the supramolecular self-assembly of 9,10-dicyanoanthracene (DCA) molecules on the Au(111) surface. Close-packed islands of DCA molecules and Au-DCA metal-organic coordination structures coexist on the Au(111) surface. Ordered DCA$_{3}$Au$_{2}$ metal-organic networks have a structure combining a honeycomb lattice of Au atoms with a kagome lattice of DCA molecules. Low-temperature STS experiments demonstrate the presence of a delocalized electronic state containing contributions from both the gold atom states and the lowest unoccupied molecular orbital of the DCA molecules. These findings are important for the future search of topological phases in metal-organic networks combining honeycomb and kagome lattices with strong spin-orbit coupling in heavy metal atoms.

We investigate the spectral evolution in different metal phthalocyanine molecules on NbSe$_2$ 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 e.g. engineered topological superconductors and spin logic devices.

Topological modes in one- and two-dimensional systems have been proposed for numerous applications utilizing their exotic electronic responses. The zero-energy, topologically protected end modes can be realized in the Su-Schrieffer-Heeger (SSH) model, which has been experimentally implemented in atomic-scale solid-state structures and in ultra-cold atomic gases. While the edge modes in the SSH model are at exactly the mid-gap energy, other paradigmatic 1D models such as trimer and coupled dimer chains have non-zero energy boundary states. However, these chains have not been realized in an atomically tuneable system that would allow explicit control of the edge modes. Here, we demonstrate atomically controlled trimer and coupled dimer chains realized using chlorine vacancies in the c$(2\times2)$ adsorption layer on Cu(100). This system allows wide tuneability of the domain wall modes that we experimentally demonstrate using low-temperature scanning tunneling microscopy (STM). In the future, these modes may be used to realize well-defined fractional charge states or find applications in exotic quantum devices with atomically well-defined geometries.

There is enormous recent interest in weak, van der Waals-type (vdW) interactions due to their fundamental relevance for two-dimensional materials and the so-called vdW heterostructures. Tackling this problem using computer simulation is very challenging due to the non-trivial, non-local nature of these interactions. We benchmark different treatments of London dispersion forces within the density functional theory (DFT) framework on hexagonal boron nitride or graphene monolayers on Ir(111) by comparing the calculated geometries to a comprehensive set of experimental data. The geometry of these systems crucially depends on the interplay between vdW interactions and wave function hybridisation, making them excellent test cases for vdW-treated DFT. Our results show strong variations in the calculated atomic geometry. While some of the approximations reproduce the experimental structure, this is rather based on \textit{a posteriori} comparison with the ``target results''. General predictive power in vdW-treated DFT is not achieved yet and might require new approaches., Comment: More or less published version, with Supporting Material

Metal-organic frameworks (MOFs) are an important class of materials that present intriguing opportunities in the fields of sensing, gas storage, catalysis, and optoelectronics. Very recently, two-dimensional (2D) MOFs have been proposed as a flexible material platform for realizing exotic quantum phases including topological and anomalous quantum Hall insulators. Experimentally, direct synthesis of 2D MOFs has been essentially confined to metal substrates, where the interaction with the substrate masks the intrinsic electronic properties of the MOF. Here, we demonstrate synthesis of 2D honeycomb metal-organic frameworks on a weakly interacting epitaxial graphene substrate. Using low-temperature scanning tunneling microscopy (STM) and atomic force microscopy (AFM) complemented by density-functional theory (DFT) calculations, we show the formation of 2D band structure in the MOF decoupled from the substrate. These results open the experimental path towards MOF-based designer quantum materials with complex, engineered electronic structures.

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 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 NbSe$_2$ using low-temperature scanning tunneling microscopy (STM) and spectroscopy (STS). 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. Our work forms an important step towards the realization of exotic topological states in designer magnetic lattices.

Molecular self-assembly is a well-known technique to create highly functional nanostructures on surfaces. Self-assembly on two-dimensional materials is a developing field and has already resulted in the discovery of several rich and interesting phenomena. Here, we review this progress with an emphasis on the electronic properties of the adsorbates and the substrate in well-defined systems, as unveiled by scanning tunneling microscopy (STM). We cover three aspects of the self-assembly. The first one focuses on non-covalent self-assembly dealing with site-selectivity due to inherent moire pattern present on 2D materials deposited on substrates. Modification of intermolecular interactions and molecule-substrate interactions influences the assembly drastically and 2D materials can also be used as a platform to carry out covalent and metal-coordinated assembly. The second part deals with the electronic properties of molecules adsorbed on 2D materials. By virtue of being inert and possessing low density of states near the Fermi level, 2D materials decouple molecules electronically from the underlying metal substrate and allow high-resolution spectroscopy and imaging of molecular orbitals. The moire pattern on the 2D materials causes site-selective gating and charging of molecules in some cases. The last section covers the effects of self-assembled organic molecules on the electronic properties of graphene as revealed by spectroscopy and electrical transport measurements. Non-covalent functionalization of 2D materials has already been applied for their application as catalysts and sensors. With the current surge of activity on building van der Waals heterostructures from 2D materials, molecular self-assembly has the potential to add an extra level of flexibility and functionality for applications ranging from flexible electronics and OLEDs to novel electronic devices and spintronics., Comment: 46 pages, 11 figures, topical review paper

Topological materials exhibit protected edge modes that have been proposed for applications in for example spintronics and quantum computation. While a number of such systems exist, it would be desirable to be able to test theoretical proposals in an artificial system that allows precise control over the key parameters of the model. The essential physics of several topological systems can be captured by tight-binding models, which can also be implemented in artificial lattices. Here, we show that this method can be realized in a vacancy lattice in a chlorine monolayer on a Cu(100) surface. We use low-temperature scanning tunneling microscopy (STM) to fabricate such lattices with atomic precision and probe the resulting local density of states (LDOS) with scanning tunneling spectroscopy (STS). We create analogues of two tight-binding models of fundamental importance: The polyacetylene (dimer) chain with topological domain wall states, and the Lieb lattice, featuring a lattice pseudospin 1 system with a flat electron band. These results provide the first steps in realizing designer quantum materials with tailored properties.

Scanning tunneling spectroscopy measures how a single electron with definite energy propagates between a sample surface and the tip of a scanning tunneling microscope. In the simplest description, the differential conductance measured is interpreted as the local density of states of the sample at the tip position. This picture, however, is insufficient in some cases, since especially smaller molecules weakly coupled with the substrate tend to have strong Coulomb interactions when an electron is inserted or removed at the molecule. We present theoretical approaches to go from the non-interacting and single-particle picture to the correlated many-body regime. The methodology is used to understand recent experiments on finite armchair graphene nanoribbons and phthalocyanines. We also theoretically discuss the strongly-correlated model system of fractional quantum Hall droplets., Comment: Submitted to Journal of Electron Spectroscopy and Related Phenomena