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35 result(s) for "Gröning, Oliver"
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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.Topological frustration in the π-electron network of the polycyclic aromatic hydrocarbon C38H18 yields unpaired electrons and a magnetically non-trivial ground state. Here, the authors synthesize this molecule, known as Clar’s goblet, on Au(111) and characterize the antiferromagnetic ground state with scanning tunnelling microscopy.
Engineering of robust topological quantum phases in graphene nanoribbons
Boundaries between distinct topological phases of matter support robust, yet exotic quantum states such as spin–momentum locked transport channels or Majorana fermions 1 – 3 . The idea of using such states in spintronic devices or as qubits in quantum information technology is a strong driver of current research in condensed matter physics 4 – 6 . The topological properties of quantum states have helped to explain the conductivity of doped trans -polyacetylene in terms of dispersionless soliton states 7 – 9 . In their seminal paper, Su, Schrieffer and Heeger (SSH) described these exotic quantum states using a one-dimensional tight-binding model 10 , 11 . Because the SSH model describes chiral topological insulators, charge fractionalization and spin–charge separation in one dimension, numerous efforts have been made to realize the SSH Hamiltonian in cold-atom, photonic and acoustic experimental configurations 12 – 14 . It is, however, desirable to rationally engineer topological electronic phases into stable and processable materials to exploit the corresponding quantum states. Here we present a flexible strategy based on atomically precise graphene nanoribbons to design robust nanomaterials exhibiting the valence electronic structures described by the SSH Hamiltonian 15 – 17 . We demonstrate the controlled periodic coupling of topological boundary states 18 at junctions of graphene nanoribbons with armchair edges to create quasi-one-dimensional trivial and non-trivial electronic quantum phases. This strategy has the potential to tune the bandwidth of the topological electronic bands close to the energy scale of proximity-induced spin–orbit coupling 19 or superconductivity 20 , and may allow the realization of Kitaev-like Hamiltonians 3 and Majorana-type end states 21 . Graphene nanoribbons are used to design robust nanomaterials with controlled periodic coupling of topological boundary states to create quasi-one-dimensional trivial and non-trivial electronic quantum phases.
Large magnetic exchange coupling in rhombus-shaped nanographenes with zigzag periphery
Nanographenes with zigzag edges are predicted to manifest non-trivial π-magnetism resulting from the interplay of concurrent electronic effects, such as hybridization of localized frontier states and Coulomb repulsion between valence electrons. This provides a chemically tunable platform to explore quantum magnetism at the nanoscale and opens avenues towards organic spintronics. The magnetic stability in nanographenes is thus far greatly limited by the weak magnetic exchange coupling, which remains below the room-temperature thermal energy. Here, we report the synthesis of large rhombus-shaped nanographenes with zigzag peripheries on gold and copper surfaces. Single-molecule scanning probe measurements show an emergent magnetic spin singlet ground state with increasing nanographene size. The magnetic exchange coupling in the largest nanographene (C70H22, containing five benzenoid rings along each edge), determined by inelastic electron tunnelling spectroscopy, exceeds 100 meV or 1,160 K, which outclasses most inorganic nanomaterials and survives on a metal electrode.Open-shell nanographenes are promising for quantum technologies, but their magnetic stability has remained limited by weak exchange coupling. Now, two large rhombus-shaped nanographenes with zigzag peripheries, one with 48 carbon atoms and the other with 70, have been synthesized on gold and copper surfaces. The 70-carbon compound exhibits a large magnetic exchange coupling exceeding 100 meV.
Controlled synthesis of single-chirality carbon nanotubes
Present preparation methods fail to meet fully the demand for structurally pure single-walled carbon nanotubes; surface-catalysed cyclodehydrogenation reactions are now shown to convert precursor molecules deposited on a platinum(111) surface into ultrashort nanotube seeds that can then be grown further into defect-free and structurally pure single-walled carbon nanotubes of single chirality. Controlled synthesis of single-chirality carbon nanotubes The electronic properties of single-walled carbon nanotubes (SWCNTs) are extraordinarily sensitive to their precise structure. To exploit their technological potential fully, samples containing only one SWCNT type are needed. Juan Ramon Sanchez-Valencia et al . have combined synthetic chemistry with materials engineering to develop a strategy that, with further optimization, could provide a route to nanotube-based materials for use in light detectors, photovoltaics, field-effect transistors and sensors. They use a surface-catalysed cyclodehydrogenation reaction to fold rationally designed precursor molecules deposited on a Pt(111) surface to produce 'end caps' that act as seeds for the growth of defect-free and structurally pure SWCNTs. The technique requires only modest temperatures and is fully compatible with today's complementary metal oxide semiconductor technologies. Cover: Konstantin Amsharov. Over the past two decades, single-walled carbon nanotubes (SWCNTs) have received much attention because their extraordinary properties are promising for numerous applications 1 , 2 . Many of these properties depend sensitively on SWCNT structure, which is characterized by the chiral index ( n , m ) that denotes the length and orientation of the circumferential vector in the hexagonal carbon lattice. Electronic properties are particularly strongly affected, with subtle structural changes switching tubes from metallic to semiconducting with various bandgaps. Monodisperse ‘single-chirality’ (that is, with a single ( n , m ) index) SWCNTs are thus needed to fully exploit their technological potential 1 , 2 . Controlled synthesis through catalyst engineering 3 , 4 , 5 , 6 , end-cap engineering 7 or cloning strategies 8 , 9 , and also tube sorting based on chromatography 10 , 11 , density-gradient centrifugation, electrophoresis and other techniques 12 , have delivered SWCNT samples with narrow distributions of tube diameter and a large fraction of a predetermined tube type. But an effective pathway to truly monodisperse SWCNTs remains elusive. The use of template molecules to unambiguously dictate the diameter and chirality of the resulting nanotube 8 , 13 , 14 , 15 , 16 holds great promise in this regard, but has hitherto had only limited practical success 7 , 17 , 18 . Here we show that this bottom-up strategy can produce targeted nanotubes: we convert molecular precursors into ultrashort singly capped (6,6) ‘armchair’ nanotube seeds using surface-catalysed cyclodehydrogenation on a platinum (111) surface, and then elongate these during a subsequent growth phase to produce single-chirality and essentially defect-free SWCNTs with lengths up to a few hundred nanometres. We expect that our on-surface synthesis approach will provide a route to nanotube-based materials with highly optimized properties for applications such as light detectors, photovoltaics, field-effect transistors and sensors 2 .
On-surface synthesis and characterization of nitrogen-substituted undecacenes
Heteroatom substitution in acenes allows tailoring of their remarkable electronic properties, expected to include spin-polarization and magnetism for larger members of the acene family. Here, we present a strategy for the on-surface synthesis of three undecacene analogs substituted with four nitrogen atoms on an Au(111) substrate, by employing specifically designed diethano-bridged precursors. A similarly designed precursor is used to synthesize the pristine undecacene molecule. By comparing experimental features of scanning probe microscopy with ab initio simulations, we demonstrate that the ground state of the synthesized tetraazaundecacene has considerable open-shell character on Au(111). Additionally, we demonstrate that the electronegative nitrogen atoms induce a considerable shift in energy level alignment compared to the pristine undecacene, and that the introduction of hydro-aza groups causes local anti-aromaticity in the synthesized compounds. Our work provides access to the precise fabrication of nitrogen-substituted acenes and their analogs, potential building-blocks of organic electronics and spintronics, and a rich playground to explore π-electron correlation. Heteroatom substitution in larger acenes represents a fundamental step towards precise engineering of the remarkable electronic properties of the acene family. Here, the authors present an on-surface synthesis strategy and detailed characterization for three undecacene analogs substituted with four nitrogen atoms.
Tailoring topological order and π-conjugation to engineer quasi-metallic polymers
Topological band theory predicts that a topological electronic phase transition between two insulators must proceed via closure of the electronic gap. Here, we use this transition to circumvent the instability of metallic phases in π-conjugated one-dimensional (1D) polymers. By means of density functional theory, tight-binding and GW calculations, we predict polymers near the topological transition from a trivial to a non-trivial quantum phase. We then use on-surface synthesis with custom-designed precursors to make polymers consisting of 1D linearly bridged acene moieties, which feature narrow bandgaps and in-gap zero-energy edge states when in the topologically non-trivial phase close to the topological transition point. We also reveal the fundamental connection between topological classes and resonant forms of 1D π-conjugated polymers.Polymers commonly are semiconducting or insulating because of a sizable energy gap in the density of states around the Fermi level. Yet, the phase transition from topologically trivial to non-trivial in on-surface synthesized π-conjugated polymers, due to a change of resonant form, stabilizes narrow bandgaps and bears in-gap zero-energy edge states in the non-trivial phase.
On-surface synthesis and characterization of individual polyacetylene chains
Polyacetylene (PA) comprises one-dimensional chains of sp 2 -hybridized carbon atoms that may take a cis or trans configuration. Owing to its simple chemical structure and exceptional electronic properties, PA is an ideal system to understand the nature of charge transport in conducting polymers. Here, we report the on-surface synthesis of both cis- and trans -PA chains and their atomic-scale characterization. The structure of individual PA chains was imaged by non-contact atomic force microscopy, which confirmed the formation of PA by resolving single chemical bond units. Angle-resolved photoemission spectroscopy suggests a semiconductor-to-metal transition through doping-induced suppression of the Peierls bond alternation of trans -PA on Cu(110). Electronically decoupled trans -PAs exhibit a band gap of 2.4 eV following copper oxide intercalation. Our study provides a platform for studying individual PA chains in real and reciprocal space, which may be further extended to study the intrinsic properties of non-linear excitons in conducting polymers. Polyacetylene is an ideal system to probe to gain a better understanding of the nature of charge transport in conducting polymers. Now, individual atomically precise polyacetylene chains have been synthesized on a copper surface and characterized using a range of techniques, revealing a doping-induced semiconductor-to-metal transition.
Switching stiction and adhesion of a liquid on a solid
Switching of static friction and adhesion of a liquid drop on a corrugated solid boron nitride surface is linked to the intercalation of hydrogen, which changes the electric field of in-plane dipole rings and thus reduces the adsorption energy. Stiction versus adhesion in a single liquid drop Stiction, or static friction, is the force required to persuade an object to start sliding across a surface. It is technologically important in devices with moving parts in contact, but is not well understood. Stijn Mertens et al . describe an inorganic model system for the study of the relationships between surface wetting, stiction, adhesion and lubrication. The system is a hexagonal boron nitride monolayer that can be electrochemically switched by intercalation of hydrogen between a corrugated and a flat morphology. The change in the surface structure of the boron nitride alters the adhesion and its balance with stiction of an aqueous drop sliding across the monolayer. The work of adhesion increases in going from the flat to the corrugated surface, whereas the stiction threshold does not change significantly. Thus the authors make a quantitative connection between the macroscopic properties of stiction and adhesion as a result of structural control at the atomic scale. When a gecko moves on a ceiling it makes use of adhesion and stiction. Stiction—static friction—is experienced on microscopic and macroscopic scales and is related to adhesion and sliding friction 1 . Although important for most locomotive processes, the concepts of adhesion, stiction and sliding friction are often only empirically correlated. A more detailed understanding of these concepts will, for example, help to improve the design of increasingly smaller devices such as micro- and nanoelectromechanical switches 2 . Here we show how stiction and adhesion are related for a liquid drop on a hexagonal boron nitride monolayer on rhodium 3 , by measuring dynamic contact angles in two distinct states of the solid–liquid interface: a corrugated state in the absence of hydrogen intercalation and an intercalation-induced flat state. Stiction and adhesion can be reversibly switched by applying different electrochemical potentials to the sample, causing atomic hydrogen to be intercalated or not. We ascribe the change in adhesion to a change in lateral electric field of in-plane two-nanometre dipole rings 4 , because it cannot be explained by the change in surface roughness known from the Wenzel model 5 . Although the change in adhesion can be calculated for the system we study 6 , it is not yet possible to determine the stiction at such a solid–liquid interface using ab initio methods. The inorganic hybrid of hexagonal boron nitride and rhodium is very stable and represents a new class of switchable surfaces with the potential for application in the study of adhesion, friction and lubrication.
Tunable topological phases in nanographene-based spin-1/2 alternating-exchange Heisenberg chains
Unlocking the potential of topological order in many-body spin systems has been a key goal in quantum materials research. Despite extensive efforts, the quest for a versatile platform enabling site-selective spin manipulation, essential for tuning and probing diverse topological phases, has persisted. Here we utilize on-surface synthesis to construct spin-1/2 alternating-exchange Heisenberg chains by covalently linking Clar’s goblets—nanographenes each hosting two antiferromagnetically coupled spins. Using scanning tunnelling microscopy, we exert atomic-scale control over chain lengths, parities and exchange-coupling terminations, and probe their magnetic response via inelastic tunnelling spectroscopy. Our investigation confirms the gapped nature of bulk excitations in the chains, known as triplons. Their dispersion relation is extracted from the spatial variation of tunnelling spectral amplitudes. Depending on the parity and termination of chains, we observe varying numbers of in-gap spin-1/2 edge excitations, reflecting the degeneracy of distinct topological ground states in the thermodynamic limit. By monitoring interactions between these edge spins, we identify the exponential decay of spin correlations. Our findings present a phase-controlled many-body platform, opening avenues toward spin-based quantum devices. Scanning probe microscopy experiments realize the alternating-exchange spin-1/2 Heisenberg model via magnetic nanographene chains. They control odd- to even-Haldane phase transitions and monitor spin–spin correlations and triplon dispersion.
Charge state-dependent symmetry breaking of atomic defects in transition metal dichalcogenides
The functionality of atomic quantum emitters is intrinsically linked to their host lattice coordination. Structural distortions that spontaneously break the lattice symmetry strongly impact their optical emission properties and spin-photon interface. Here we report on the direct imaging of charge state-dependent symmetry breaking of two prototypical atomic quantum emitters in mono- and bilayer MoS 2 by scanning tunneling microscopy (STM) and non-contact atomic force microscopy (nc-AFM). By changing the built-in substrate chemical potential, different charge states of sulfur vacancies (Vac S ) and substitutional rhenium dopants (Re Mo ) can be stabilized. Vac S − 1 as well as Re Mo 0 and Re Mo − 1 exhibit local lattice distortions and symmetry-broken defect orbitals attributed to a Jahn-Teller effect (JTE) and pseudo-JTE, respectively. By mapping the electronic and geometric structure of single point defects, we disentangle the effects of spatial averaging, charge multistability, configurational dynamics, and external perturbations that often mask the presence of local symmetry breaking. The microscopic structure of quantum defects in 2D materials is crucial to understand their optical properties and spin-photon interface. Here, the authors report the direct imaging of charge state-dependent symmetry breaking of sulfur vacancies and rhenium dopants in 2D MoS 2 , showing evidence of a Jahn-Teller effect.