Tuneable Current Rectification Through a Designer Graphene Nanoribbon.

Unimolecular current rectifiers are fundamental building blocks in organic electronics. Rectifying behavior has been identified in numerous organic systems due to electron-hole asymmetries of orbital levels interfaced by a metal electrode. As a consequence, the rectifying ratio (RR) determining the diode efficiency remains fixed for a chosen molecule-metal interface. Here, a mechanically tunable molecular diode exhibiting an exceptionally large rectification ratio (>105) and reversible direction is presented. The molecular system comprises a seven-armchair graphene nanoribbon (GNR) doped with a single unit of substitutional diboron within its structure, synthesized with atomic precision on a gold substrate by on-surface synthesis. The diboron unit creates half-populated in-gap bound states and splits the GNR frontier bands into two segments, localizing the bound state in a double barrier configuration. By suspending these GNRs freely between the tip of a low-temperature scanning tunneling microscope and the substrate, unipolar hole transport is demonstrated through the boron in-gap state's resonance. Strong current rectification is observed, associated with the varying widths of the two barriers, which can be tuned by altering the distance between tip and substrate. This study introduces an innovative approach for the precise manipulation of molecular electronic functionalities, opening new avenues for advanced applications in organic electronics.

Ferromagnetic Order in 2D Layers of Transition Metal Dichlorides.

Magnetism in two dimensions is traditionally considered an exotic phase mediated by spin fluctuations, but far from collinearly ordered in the ground state. Recently, 2D magnetic states have been discovered in layered van der Waals compounds. Their robust and tunable magnetic state by material composition, combined with reduced dimensionality, foresee a strong potential as a key element in magnetic devices. Here, a class of 2D magnets based on metallic chlorides is presented. The magnetic order survives on top of a metallic substrate, even down to the monolayer limit, and can be switched from perpendicular to in-plane by substituting the metal ion from iron to nickel. Using functionalized STM tips as magnetic sensors, local exchange fields are identified, even in the absence of an external magnetic field. Since the compounds are processable by molecular beam epitaxy techniques, they provide a platform with large potential for incorporation into current device technologies.

From Solution to Surface: Persistence of the Diradical Character of a Diindenoanthracene Derivative on a Metallic Substrate.

Organic diradicals are envisioned as elementary building blocks for designing a new generation of spintronic devices and have been used in constructing prototypical field effect transistors and nonlinear optical devices. Open-shell systems, however, are also reactive, thus requiring design strategies to "protect" their radical character from the environment, especially when they are embedded in solid-state devices. Here, we report the persistence on a metallic surface of the diradical character of a diindeno[b,i]anthracene (DIAn) core protected by bulky end-groups. Our scanning tunneling spectroscopy measurements on single-molecules detected singlet-triplet excitations that were absent for DIAn species packed in assembled structures. Density functional theory simulations unravel that the molecular geometry on the metal substrate can crucially modify the value of the singlet-triplet gap via the delocalization of the radical sites. The persistence of the diradical character over metallic substrates is a promising finding for integrating radical-based materials into functional devices.

On-Surface Synthesis and Characterization of a High-Spin Aza-[5]-Triangulene.

Triangulenes are a class of open-shell triangular graphene flakes with total spin increasing with their size. In the last years, on-surface-synthesis strategies have permitted fabricating and engineering triangulenes of various sizes and structures with atomic precision. However, direct proof of the increasing total spin with their size remains elusive. In this work, we report the combined in-solution and on-surface synthesis of a large nitrogen-doped triangulene (aza-[5]-triangulene) on a Au(111) surface, and the detection of its high-spin ground state. Bond-resolved scanning tunneling microscopy images uncovered radical states distributed along the zigzag edges, which were detected as weak zero-bias resonances in scanning tunneling spectra. These spectral features reveal the partial Kondo screening of a high-spin state. Through a combination of several simulation tools, we find that the observed distribution of radical states is explained by a quintet ground state (S=2), instead of the quartet state (S=3/2) expected for the neutral species. This confirms that electron transfer to the metal substrate raises the spin of the ground state. We further provide a qualitative description of the change of (anti)aromaticity introduced by N-substitution, and its role in the charge stabilization on a surface, resulting in an S=2 aza-triangulene on Au(111).

Cooper Pair Excitation Mediated by a Molecular Quantum Spin on a Superconducting Proximitized Gold Film.

Breaking a correlated pair in a superconductor requires an even number of fermions providing at least twice the pairing energy Δ. Here, we show that a single tunneling electron can also excite a pair breaking excitation in a proximitized gold film in the presence of magnetic impurities. Combining scanning tunneling spectroscopy with theoretical modeling, we map the excitation spectrum of an Fe-porphyrin molecule on the Au/V(100) proximitized surface into a manifold of entangled Yu-Shiba-Rusinov and spin excitations. Pair excitations emerge in the tunneling spectra as peaks outside the spectral gap only in the strong coupling regime, where the presence of a bound quasiparticle in the ground state ensures the even fermion parity of the excitation. Our results unravel the quantum nature of magnetic impurities on superconductors and demonstrate that pair excitations unequivocally reveal the parity of the ground state.

Addressing Electron Spins Embedded in Metallic Graphene Nanoribbons.

Spin-hosting graphene nanostructures are promising metal-free systems for elementary quantum spintronic devices. Conventionally, spins are protected from quenching by electronic band gaps, which also hinder electronic access to their quantum state. Here, we present a narrow graphene nanoribbon substitutionally doped with boron heteroatoms that combines a metallic character with the presence of localized spin 1/2 states in its interior. The ribbon was fabricated by on-surface synthesis on a Au(111) substrate. Transport measurements through ribbons suspended between the tip and the sample of a scanning tunneling microscope revealed their ballistic behavior, characteristic of metallic nanowires. Conductance spectra show fingerprints of localized spin states in the form of Kondo resonances and inelastic tunneling excitations. Density functional theory rationalizes the metallic character of the graphene nanoribbon due to the partial depopulation of the valence band induced by the boron atoms. The transferred charge builds localized magnetic moments around the boron atoms. The orthogonal symmetry of the spin-hosting state's and the valence band's wave functions protects them from mixing, maintaining the spin states localized. The combination of ballistic transport and spin localization into a single graphene nanoribbon offers the perspective of electronically addressing and controlling carbon spins in real device architectures.

Extending the Spin Excitation Lifetime of a Magnetic Molecule on a Proximitized Superconductor.

Molecular spins on surfaces potentially used in quantum information processing and data storage require long spin excitation lifetimes. Normally, coupling of the molecular spin with the conduction electrons of metallic surfaces causes fast relaxation of spin excitations. However, the presence of superconducting pairing effects in the substrate can protect the excited spin from decaying. In this work, we show that a proximity-induced superconducting gold film can sustain spin excitations of a FeTPP-Cl molecule for more than 80 ns. This long value was determined by studying inelastic spin excitations of the S = 5/2 multiplet of FeTPP-Cl on Au films over V(100) using scanning tunneling spectroscopy. The spin lifetime decreases with increasing film thickness, along with the decrease of the effective superconducting gap. Our results elucidate the use of proximitized gold electrodes for addressing quantum spins on surfaces, envisioning new routes for tuning the value of their spin lifetime.

Aza-Triangulene: On-Surface Synthesis and Electronic and Magnetic Properties.

Nitrogen heteroatom doping into a triangulene molecule allows tuning its magnetic state. However, the synthesis of the nitrogen-doped triangulene (aza-triangulene) has been challenging. Herein, we report the successful synthesis of aza-triangulene on the Au(111) and Ag(111) surfaces, along with their characterizations by scanning tunneling microscopy and spectroscopy in combination with density functional theory (DFT) calculations. Aza-triangulenes were obtained by reducing ketone-substituted precursors. Exposure to atomic hydrogen followed by thermal annealing and, when necessary, manipulations with the scanning probe afforded the target product. We demonstrate that on Au(111), aza-triangulene donates an electron to the substrate and exhibits an open-shell triplet ground state. This is derived from the different Kondo resonances of the final aza-triangulene product and a series of intermediates on Au(111). Experimentally mapped molecular orbitals match with DFT-calculated counterparts for a positively charged aza-triangulene. In contrast, aza-triangulene on Ag(111) receives an extra electron from the substrate and displays a closed-shell character. Our study reveals the electronic properties of aza-triangulene on different metal surfaces and offers an approach for the fabrication of new hydrocarbon structures, including reactive open-shell molecules.

On-Surface Synthesis and Collective Spin Excitations of a Triangulene-Based Nanostar.

Triangulene nanographenes are open-shell molecules with predicted high spin state due to the frustration of their conjugated network. Their long-sought synthesis became recently possible over a metal surface. Here, we present a macrocycle formed by six [3]triangulenes, which was obtained by combining the solution synthesis of a dimethylphenyl-anthracene cyclic hexamer and the on-surface cyclodehydrogenation of this precursor over a gold substrate. The resulting triangulene nanostar exhibits a collective spin state generated by the interaction of its 12 unpaired π-electrons along the conjugated lattice, corresponding to the antiferromagnetic ordering of six S=1 sites (one per triangulene unit). Inelastic electron tunneling spectroscopy resolved three spin excitations connecting the singlet ground state with triplet states. The nanostar behaves close to predictions from the Heisenberg model of an S=1 spin ring, representing a unique system to test collective spin modes in cyclic systems.

Topological phase transition in chiral graphene nanoribbons: from edge bands to end states.

Precise control over the size and shape of graphene nanostructures allows engineering spin-polarized edge and topological states, representing a novel source of non-conventional π-magnetism with promising applications in quantum spintronics. A prerequisite for their emergence is the existence of robust gapped phases, which are difficult to find in extended graphene systems. Here we show that semi-metallic chiral GNRs (chGNRs) narrowed down to nanometer widths undergo a topological phase transition. We fabricated atomically precise chGNRs of different chirality and size by on surface synthesis using predesigned molecular precursors. Combining scanning tunneling microscopy (STM) measurements and theory simulations, we follow the evolution of topological properties and bulk band gap depending on the width, length, and chirality of chGNRs. Our findings represent a new platform for producing topologically protected spin states and demonstrate the potential of connecting chiral edge and defect structure with band engineering.

Noncollinear Magnetic Order in Two-Dimensional NiBr2 Films Grown on Au(111).

Metal halides are a class of layered materials with promising electronic and magnetic properties persisting down to the two-dimensional limit. While most recent studies focused on the trihalide components of this family, the rather unexplored metal dihalides are also van der Waals layered systems with distinctive magnetic properties. Here we show that the dihalide NiBr2 grows epitaxially on a Au(111) substrate and exhibits semiconducting and magnetic behavior starting from a single layer. Through a combination of a low-temperature scanning-tunneling microscopy, low-energy electron diffraction, X-ray photoelectron spectroscopy, and photoemission electron microscopy, we identify two competing layer structures of NiBr2 coexisting at the interface and a stoichiometrically pure layer-by-layer growth beyond. Interestingly, X-ray absorption spectroscopy measurements revealed a magnetically ordered state below 27 K with in-plane magnetic anisotropy and zero-remanence in the single layer of NiBr2/Au(111), which we attribute to a noncollinear magnetic structure. The combination of such two-dimensional magnetic order with the semiconducting behavior down to the 2D limit offers the attractive perspective of using these films as ultrathin crystalline barriers in tunneling junctions and low-dimensional devices.

Coupled Yu-Shiba-Rusinov States Induced by a Many-Body Molecular Spin on a Superconductor.

A magnetic impurity on a superconductor induces Yu-Shiba-Rusinov (YSR) bound states, detected by tunneling spectroscopy as long-lived quasiparticle excitations inside the superconducting gap. Coupled YSR states constitute basic elements to engineer artificial superconducting states, but their substrate-mediated interactions are generally weak. In this Letter, we report that intramolecular (Hund's-like) exchange interactions produce coupled YSR states across a molecular platform. We measured YSR spectra along a magnetic iron-porphyrin on Pb(111) and found evidence of two distinct interaction channels, which invert their particle-hole asymmetry across the molecule. Numerical calculations show that the identical YSR asymmetry pattern of the two channels is caused by two spin-hosting orbitals with opposite potential scattering and coupled strongly. Both channels can be similarly excited by tunneling electrons into each orbital, depicting a new scenario for entangled superconducting bound states using molecular platforms.

Magnetism of Topological Boundary States Induced by Boron Substitution in Graphene Nanoribbons.

Graphene nanoribbons (GNRs), low-dimensional platforms for carbon-based electronics, show the promising perspective to also incorporate spin polarization in their conjugated electron system. However, magnetism in GNRs is generally associated with localized states around zigzag edges, difficult to fabricate and with high reactivity. Here we demonstrate that magnetism can also be induced away from physical GNR zigzag edges through atomically precise engineering topological defects in its interior. A pair of substitutional boron atoms inserted in the carbon backbone breaks the conjugation of their topological bands and builds two spin-polarized boundary states around them. The spin state was detected in electrical transport measurements through boron-substituted GNRs suspended between the tip and the sample of a scanning tunneling microscope. First-principle simulations find that boron pairs induce a spin 1, which is modified by tuning the spacing between pairs. Our results demonstrate a route to embed spin chains in GNRs, turning them into basic elements of spintronic devices.

Visualization of Multifractal Superconductivity in a Two-Dimensional Transition Metal Dichalcogenide in the Weak-Disorder Regime.

Eigenstate multifractality is a distinctive feature of noninteracting disordered metals close to a metal-insulator transition, whose properties are expected to extend to superconductivity. While multifractality in three dimensions (3D) only develops near the critical point for specific strong-disorder strengths, multifractality in 2D systems is expected to be observable even for weak disorder. Here we provide evidence for multifractal features in the superconducting state of an intrinsic, weakly disordered single-layer NbSe2 by means of low-temperature scanning tunneling microscopy/spectroscopy. The superconducting gap, characterized by its width, depth, and coherence peaks' amplitude, shows a characteristic spatial modulation coincident with the periodicity of the quasiparticle interference pattern. The strong spatial inhomogeneity of the superconducting gap width, proportional to the local order parameter in the weak-disorder regime, follows a log-normal statistical distribution as well as a power-law decay of the two-point correlation function, in agreement with our theoretical model. Furthermore, the experimental singularity spectrum f(α) shows anomalous scaling behavior typical from 2D weakly disordered systems.

Uncovering the Triplet Ground State of Triangular Graphene Nanoflakes Engineered with Atomic Precision on a Metal Surface.

Graphene can develop large magnetic moments in custom-crafted open-shell nanostructures such as triangulene, a triangular piece of graphene with zigzag edges. Current methods of engineering graphene nanosystems on surfaces succeeded in producing atomically precise open-shell structures, but demonstration of their net spin remains elusive to date. Here, we fabricate triangulenelike graphene systems and demonstrate that they possess a spin S=1 ground state. Scanning tunneling spectroscopy identifies the fingerprint of an underscreened S=1 Kondo state on these flakes at low temperatures, signaling the dominant ferromagnetic interactions between two spins. Combined with simulations based on the meanfield Hubbard model, we show that this S=1 π paramagnetism is robust and can be turned into an S=1/2 state by additional H atoms attached to the radical sites. Our results demonstrate that π paramagnetism of high-spin graphene flakes can survive on surfaces, opening the door to study the quantum behavior of interacting π spins in graphene systems.

Band Depopulation of Graphene Nanoribbons Induced by Chemical Gating with Amino Groups.

The electronic properties of graphene nanoribbons (GNRs) can be precisely tuned by chemical doping. Here we demonstrate that amino (NH2) functional groups attached at the edges of chiral GNRs (chGNRs) can efficiently gate the chGNRs and lead to the valence band (VB) depopulation on a metallic surface. The NH2-doped chGNRs are grown by on-surface synthesis on Au(111) using functionalized bianthracene precursors. Scanning tunneling spectroscopy resolves that the NH2 groups significantly upshift the bands of chGNRs, causing the Fermi level crossing of the VB onset of chGNRs. Through density functional theory simulations we confirm that the hole-doping behavior is due to an upward shift of the bands induced by the edge NH2 groups.

Switching the Spin on a Ni Trimer within a Metal-Organic Motif by Controlling the On-Top Bromine Atom.

Controlling the spin of metal atoms embedded in molecular systems is a key step toward the realization of molecular electronics and spintronics. Many efforts have been devoted to explore the influencing factors dictating the survival or quenching of a magnetic moment in a metal-organic molecule, and among others, the spin control by axial ligand attachments is the most promising. Herein, from the interplay of high-resolution scanning tunneling microscopy imaging/manipulation and scanning tunneling spectroscopy measurements together with density functional theory calculations, we successfully demonstrate that a Ni trimer within a metal-organic motif acquires a net spin promoted by the adsorption of an on-top Br atom. The spin localization in the trimetal centers bonded to Br was monitored via the Kondo effect. The removal of the Br ligand resulted in the switch from a Kondo ON to a Kondo OFF state. The magnetic state induced by the Br ligand is theoretically attributed to the enhanced Br 4pz and Ni 3dz2 states due to the charge redistribution. The manipulation strategy reported here provides the possibility to explore potential applications of spin-tunable structures in spintronic devices.

Hierarchy in the Halogen Activation During Surface-Promoted Ullmann Coupling.

Within the collection of surface-supported reactions currently accessible for the production of extended molecular nanostructures under ultra-high vacuum, Ullmann coupling has been the most successful in the controlled formation of covalent single C-C bonds. Particularly advanced control of this synthetic tool has been obtained by means of hierarchical reactivity, commonly achieved by the use of different halogen atoms that consequently display distinct activation temperatures. Here we report on the site-selective reactivity of certain carbon-halogen bonds. We use precursor molecules halogenated with bromine atoms at two non-equivalent carbon atoms and found that the Ullmann coupling occurs on Au(111) with a remarkable predilection for one of the positions. Experimental evidence is provided by means of scanning tunneling microscopy and core level photoemission spectroscopy, and a rationalized understanding of the observed preference is obtained from density functional theory calculations.

Electrically Addressing the Spin of a Magnetic Porphyrin through Covalently Connected Graphene Electrodes.

We report on the fabrication and transport characterization of atomically precise single-molecule devices consisting of a magnetic porphyrin covalently wired by graphene nanoribbon electrodes. The tip of a scanning tunneling microscope was utilized to contact the end of a GNR-porphyrin-GNR hybrid system and create a molecular bridge between the tip and sample for transport measurements. Electrons tunneling through the suspended molecular heterostructure excited the spin multiplet of the magnetic porphyrin. The detachment of certain spin centers from the surface shifted their spin-carrying orbitals away from an on-surface mixed-valence configuration, recovering its original spin state. The existence of spin-polarized resonances in the free-standing systems and their electrical addressability is the fundamental step in the utilization of carbon-based materials as functional molecular spintronics systems.

Single spin localization and manipulation in graphene open-shell nanostructures.

Turning graphene magnetic is a promising challenge to make it an active material for spintronics. Predictions state that graphene structures with specific shapes can spontaneously develop magnetism driven by Coulomb repulsion of π-electrons, but its experimental verification is demanding. Here, we report on the observation and manipulation of individual magnetic moments in graphene open-shell nanostructures on a gold surface. Using scanning tunneling spectroscopy, we detect the presence of single electron spins localized around certain zigzag sites of the carbon backbone via the Kondo effect. We find near-by spins coupled into a singlet ground state and quantify their exchange interaction via singlet-triplet inelastic electron excitations. Theoretical simulations picture how electron correlations result in spin-polarized radical states with the experimentally observed spatial distributions. Extra hydrogen atoms bound to radical sites quench their magnetic moment and switch the spin of the nanostructure in half-integer amounts. Our work demonstrates the intrinsic π-paramagnetism of graphene nanostructures.