Scanning Tunneling Research Articles

Highly Selective On‐Surface Dehydrogenative Aromatization of n‐Hexyl to Phenyl Substituents

AbstractDehydrogenative aromatization of alkyl substituents represents a powerful approach to aryl‐substituted functional molecules. However, the inertness of alkyl groups and the need for harsh reaction conditions accompanied by low product selectivity hamper its widespread applications. Here, we demonstrate the highly selective on‐surface thermal aromatization of n‐hexyl substituents on polycyclic aromatic hydrocarbons (PAHs) to their phenyl‐substituted analogues under mild conditions. After depositing two representative precursor molecules, n‐hexyl‐substituted hexaphenylbenzene (HPB‐Hex) and bianthryl octacarboxylic tetraimide (BATI‐Hex), onto a pre‐heated Au(111) substrate, dehydroaromatization of the peripheral n‐hexyl groups into phenyl rings occurs, following the planarization of hexaphenylbenzene and bianthryl core. This process involves sequential intramolecular C−C bond rotations, dehydrogenation, and cyclodehydrogenation reactions, yielding phenyl‐substituted hexabenzocoronene (HBC‐Ph) and bisanthene octacarboxylic tetraimides (BSTI‐Ph). The reaction sequences were monitored using scanning tunneling microscopy (STM) and bond‐resolved non‐contact atomic force microscopy (nc‐AFM), offering structural proof of both intermediates and final products. These experimental techniques were complemented by density functional theory (DFT) simulations, which facilitated the detection of crucial steps in the conversion of n‐hexyl to phenyl groups. Moreover, the effect of alkyl aromatization on the electronic properties of the newly formed aromatic hydrocarbons was elucidated using scanning tunneling spectroscopy (STS).

Surface superconductivity in the topological Weyl semimetal t-PtBi2.

Topological superconductivity is a promising concept for generating fault-tolerant qubits. Early experimental studies looked at hybrid systems and doped intrinsic topological or superconducting materials at very low temperatures. However, higher critical temperatures are indispensable for technological exploitation. Recent angle-resolved photoemission spectroscopy results have revealed that superconductivity in the type-I Weyl semimetal-trigonal PtBi2 (t-PtBi2)-is located at the Fermi-arc surface states, which renders the material a potential candidate for intrinsic topological superconductivity. Here we show, using scanning tunnelling microscopy and spectroscopy, that t-PtBi2 presents surface superconductivity at elevated temperatures (5 K). The gap magnitude is elusive: it is spatially inhomogeneous and spans from 0 to 20 meV. In particular, the large gap value and the shape of the quasiparticle excitation spectrum resemble the phenomenology of high-Tc superconductors. To our knowledge, this is the largest superconducting gap so far measured in a topological material. Moreover, we show that the superconducting state at 5 K persists in magnetic fields up to 12 T.

Cooperative Use of N-Heterocyclic Carbenes and Thiols on a Silver Surface: A Synergetic Approach to Surface Modification.

Surface modification through the formation of a self-assembled monolayer (SAM) can effectively engineer the physicochemical properties of the surface/material. However, the precise design of multifunctional SAMs at the molecular level is still a major challenge. Here, we jointly use N-heterocyclic carbenes (NHCs) and thiols to form multifunctional hetero-SAM systems that demonstrate excellent chemical stability, electrical conductivity, and, in silico, catalytic activity. This synergistic effect is facilitated by the high surface mobility and electron-rich nature of NHCs, combined with the strong binding strength of thiols. Scanning tunneling microscopy, electrical conductivity, and scanning electron microscope measurements, as well as density functional theory calculations, were employed to explore the synergistic interactions in the supramolecular SAMs. The van der Waals integration of ballbot-type NHCs and thiols enables the SAMs to exhibit both superior surface anticorrosion properties (attributing to the shift in the d-band center) and low surface resistance originating from the band alignment. Moreover, we find that the deposition sequence of flat-lying NHCs and thiols results in SAMs with different configurations, which can further tune the mechanistic pathway in silico in the acetylene hydrogenation process. Our results provide essential molecular insights into the local electronic control of the new SAM/metal interface and the high stability of the emergent multifunctionality (NHC/thiol)-SAMs forming self-assembled lamellae structures in the nanometer regime.

Moiré plane wave expansion model for scanning tunneling microscopy simulations of incommensurate two-dimensional materials

Moiré plane wave expansion model for scanning tunneling microscopy simulations of incommensurate two-dimensional materials

Role of Metal-Oxide Interfaces in Methanol Decomposition: Reaction of Methanol on CeO2/Ag(111) Inverse Model Catalysts.

Metal-oxide interfaces play a critical role in catalytic processes, such as methanol adsorption and decomposition reactions. In this work, we investigated methanol reactions on the inverse model CeO2/Ag(111) catalyst surfaces, i.e., submonolayer CeO2 films on Ag(111), under ultrahigh vacuum (UHV) conditions to specially address the role of CeO2-Ag interface in the catalytic methanol decomposition reactions. Using scanning tunneling microscopy (STM), low-energy electron diffraction (LEED), and synchrotron radiation photoemission spectroscopy (SRPES), we found that, at the submonolayer ceria coverages, the CeO2 nanoislands exhibit a hexagonal CeO2(111) lattice with fully oxidized Ce4+ on Ag(111). At higher ceria coverages, multilayer ceria nanoislands form on the Ag(111) surface instead of a well-ordered film. A combination of temperature-programmed desorption (TPD) and SRPES reveals that methanol adsorbs dissociatively on the CeO2/Ag(111) surfaces at 110 K, resulting in the formation of methoxy groups. These methoxy groups subsequently decompose via two pathways: (i) interaction with lattice oxygen to produce formate species at 230 K, which then decompose to CO, and (ii) direct dehydrogenation of methoxy to formaldehyde. Notably, the surface with submonolayer CeO2 film on Ag(111) demonstrates low-temperature reactivity (440 K) for methoxy dehydrogenation to formaldehyde, which occurs at a much lower temperature, compared to the surface of multilayer CeO2 on Ag(111) surface (530 K). This finding emphasizes that the CeO2-Ag(111) interfaces provide unique active sites for methoxy dehydrogenation reactions.

Coverage- and temperature-induced self-metalation of tetraphenyltransdibenzoporphyrin on Cu(111).

We have investigated the adsorption and self-metalation of free-base tetraphenyltransdibenzoporphyrin (2H-TPtdBP) on Cu(111) as a function of coverage and temperature using scanning tunneling microscopy, X-ray photoelectron spectroscopy, temperature programmed desorption, and density-functional theory calculations. At low coverages (<0.16 molecules/nm2), we observe isolated individual molecules with an inverted conformation and no self-metalation up to 363 K. At higher coverages, both the formation of ordered islands and self-metalation are observed over time already at room temperature, and accelerate upon heating to 363 K. At 423 K, complete self-metalation occurs for all coverages up to the completed first layer. By comparing our results for 2H-TPtdBP to the existing literature on other tetraphenyl-based porphyrins, we demonstrate how adsorption and self-metalation can be tailored by the choice of substituents.&#xD.

Nanometer-Scale 1D Negative Differential Resistance Channels in Van Der Waals Layers.

Negative differential resistance (NDR) is the key feature of resonant tunneling diodes exploited for high-frequency and low-power devices and recent studies have focused on NDR in van der Waals heterostructures and nanoscale materials. Here, strong NDR confined along a 1-nm-wide 1D channel within a van der Waals layer 1T-TaS2 is reported. Using scanning tunneling microscopy, a double 1D NDR channel formed along the sides of a charge-density-wave domain wall of 1T-TaS2 is found. The density functional theory calculation elucidates that the strong local band-bending at the domain wall and the interlayer orbital overlap cooperate to bring about 1D NDR channels. Furthermore, the NDR is well controlled by changing the tunneling junction distance. This result would be important for nanoscale device applications based on strong nonlinear resistance within van der Waals material architectures.

Adsorption Structure-Activity Correlation in the Photocatalytic Chemistry of Methanol and Water on TiO2(110).

ConspectusPhotocatalysis, a process involving light absorption (band gap excitation), charge separation, interfacial charge transfer, and surface redox reactions, has attracted intensive attention because of the potential applications in solar to fuel conversion. Despite the great efforts devoted to the design of materials and optimization of charge separation and overall efficiency, the molecular mechanism of photocatalytic reactions, for example, water oxidation, is still unclear, mainly because of the complexity of powder catalysts and the aqueous environment which prevent the direct experimental detection of adsorption sites, surface species, and charge/energy transfer dynamics. Without direct evidence, the charge transfer and elementary reaction steps remain elusive, and misleading conclusions are sometimes drawn. For instance, the positively charged 5-fold coordinated Ti sites (Ti5cs) on TiO2 surfaces are argued to propel holes and therefore cannot be active sites for oxidative reactions, regardless of the demonstration by scanning tunneling microscopy (STM). Direct site-specific measurements are thus highly demanded. Surface science studies, which rely on well-defined single crystals and ultrahigh vacuum based techniques, can identify the active sites and active species at the catalyst surfaces and measure the interfacial electronic structure and energy of desorbing species for charge transfer analysis, providing direct evidence for investigating the photocatalytic reaction mechanism at the molecular level.In this Account, the elementary photocatalytic chemistry of methanol and water on TiO2, which are investigated by surface science techniques such as atom-resolved STM, ensemble-averaged mass spectrometer based temperature-programmed desorption/time-of-flight spectroscopy, and photoelectron spectroscopy in combination with theoretical calculations, will be described. Both methanol and water can be photocatalytically oxidized at Ti5cs, producing adsorbed formaldehyde and gaseous •OH radicals, respectively, under ultraviolet (UV) light irradiation. The photocatalytic activity shows salient adsorption structure including adsorption site (terminal/bridging), adsorption state (molecular/dissociative) and adsorption configuration (monomer/cluster) dependence, which comes from the ability to generate terminal anions which are capable of capturing photogenerated holes and exhibit superior photocatalytic activity over their parent molecules. These studies reveal the origin of the correlation between photocatalytic activity and adsorption structure of CH3OH and H2O on TiO2 surfaces and suggest that the simple criteria widely used to analyze the feasibility of charge transfer, i.e., the relative position of the band edges and the molecular orbitals of adsorbates, should be replaced by the change of Gibbs free energy of the charge trapping reaction from the thermodynamic point of view. These results contribute to the fundamental understanding of photocatalysis. Based on our research, future state-resolved and time-resolved studies can provide deeper insight into the charge and energy transfer and transient intermediate species, which will benefit the depiction of the overall photocatalytic reactions, for example, the photocatalyzed oxygen evolution reaction from water.

Layer-dependent evolution of electronic structures and correlations in rhombohedral multilayer graphene.

The recent discovery of superconductivity and magnetism in trilayer rhombohedral graphene (RG) establishes an ideal, untwisted platform to study strong correlation electronic phenomena. However, the correlated effects in multilayer RG have received limited attention, and, particularly, the evolution of the correlations with increasing layer number remains an unresolved question. Here we show the observation of layer-dependent electronic structures and correlations-under surprising liquid nitrogen temperature-in RG multilayers from 3 to 9 layers by using scanning tunnelling microscopy and spectroscopy. We explicitly determine layer-enhanced low-energy flat bands and interlayer coupling strengths. The former directly demonstrates the further flattening of low-energy bands in thicker RG, and the latter indicates the presence of varying interlayer interactions in RG multilayers. Moreover, we find significant splittings of the flat bands, ranging from ~50 meV to 80 meV, at 77 K when they are partially filled, indicating the emergence of interaction-induced strongly correlated states. Particularly, the strength of the correlated states is notably enhanced in thicker RG and reaches its maximum in the six-layer, validating directly theoretical predictions and establishing abundant new candidates for strongly correlated systems. Our results provide valuable insights into the layer dependence of the electronic properties in RG and demonstrate it as a suitable system for investigating robust and highly accessible correlated phases.

P-d Correlation-Determined Charge Order Stiffness and Corresponding Quantum Melting in Monolayer 1T-TiSe2.

1T-TiSe2, a promising candidate of the sought-after excitonic insulator, possesses an enigmatic charge density wave (CDW) order of which the microscopic origin is formidable to settle owing to the chicken-and-egg entanglement between the electron and lattice degrees of freedom. Its CDW experiences an intriguing but elusive quantum melting and eventually enters the superconducting phase under metal intercalation, suggesting the possible role of melted-order fluctuation in gluing the electron paring. Employing the spectroscopic imaging scanning tunneling microscope (STM), we access the pure electronic behavior by visualizing the CDW melting process of monolayer 1T-TiSe2 in both the space and energy-band dimensions. In real space, the native lattice imperfections disturb the local order parameter and stimulate the melting of CDW. In energy-band space, different states exhibit varying stiffness against the melting stimuli, yielding distinctive melted textures. The evolution of CDW topological defects and the structure factor in the quantum melting process provide a straightforward avenue to evaluate the CDW coherency, which shows that the CDW stiffness scales with the strength of the p-d Coulomb correlation. Our study reveals the quantum melting of CDW with an altering band-orbital-correlation character and puts compelling emphasis on the indispensable role of excitonic interaction in stabilizing the charge order of monolayer TiSe2.

Tuning the Magnetism in Ultrathin CrxTey Films by Lattice Dimensionality

Abstract2D magnetic crystals with atomic thickness exhibit intriguing physical properties, which have attracted considerable research interest in the related materials’ family, both in fundamental research and in developing spintronic devices. The recent discovery of some non‐van der Waals 2D magnetic crystals expands the systems. Nevertheless, the relationship between the dimensionality of microscopic magnetic exchange interactions and macroscopic magnetic properties at the 2D limit remains to be fully elucidated. Here, we have fabricated mono‐phased continuous ultrathin CrTe2 and Cr3Te4 films by molecular beam epitaxy and elucidated the diverse magnetism tuned by the dimensionality of exchange interactions by a joint study of spin‐polarized scanning tunneling microscopy, magnetization, magneto‐transport measurements, and density functional theory calculations. The transition from a zigzag‐antiferromagnetic order in the monolayer CrTe2 to a ferromagnetic (FM) order in the second‐layer CrTe2 is confirmed, which is driven by their varied in‐plane lattice constants induced change of 2D exchange interactions. A robust FM state with large perpendicular magnetic anisotropy in Cr3Te4 is observed, originating from its strong 3D exchange interactions. The observed evolution of magnetism demonstrates that the dimensionality of magnetic exchange interactions strongly influences magnetism even at the 2D limit.

Molecular beam epitaxy and band structures of type-II antiferromagnetic semiconductor EuTe thin films

The rare-earth Eu-based compounds with a unique half-filled 4f orbital have attracted an amount of research interest recently. Here, we synthesized EuTe(001) single-crystal thin films on SrTiO3(001) substrate via molecular beam epitaxy (MBE). The scanning tunneling microscopy and x-ray diffraction results indicate that the grown EuTe thin films orientated as EuTe[100]//SrTiO3[110] in plane. In the angle-resolved photoemission spectroscopic (ARPES) measurements, the grown EuTe films show a semiconductive band structure with the valence band maximum lying on the center point of the Brillouin zone. The bandgap size of EuTe was further identified by the optical transmission spectra as 2.2 eV. The antiferromagnetic transition temperature of the grown EuTe film is 10.5 K measured by a superconductive quantum interference device (SQUID). Our results provide important information on the fundamental electronic structures for the further research and applications of the Eu-based compounds.

Fluorescence from a single-molecule probe directly attached to a plasmonic STM tip

The scanning tunneling microscope (STM) provides access to atomic-scale properties of a conductive sample. While single-molecule tip functionalization has become a standard procedure, fluorescent molecular probes remained absent from the available tool set. Here, the plasmonic tip of an STM is functionalized with a single fluorescent molecule and is scanned on a plasmonic substrate. The tunneling current flowing through the tip-molecule-substrate junction generates a narrow-line emission of light corresponding to the fluorescence of the negatively charged molecule suspended at the apex of the tip, i.e., the emission of the excited molecular anion. The fluorescence of this molecular probe is recorded for tip-substrate nanocavities featuring different plasmonic resonances, for different tip-substrate distances and applied bias voltages, and on different substrates. We demonstrate that the width of the emission peak can be used as a probe of the exciton-plasmon coupling strength and that the energy of the emitted photons is governed by the molecule interactions with its environment. Additionally, we theoretically elucidate why the direct contact of the suspended molecule with the metallic tip does not totally quench the radiative emission of the molecule.

Absence of bulk charge density wave order in the normal state of UTe2

A spatially modulated superconducting state, known as pair density wave (PDW), is a tantalizing state of matter with unique properties. Recent scanning tunneling microscopy (STM) studies revealed that spin-triplet superconductor UTe2 hosts an unprecedented spin-triplet, multi-component PDW whose three wavevectors are indistinguishable from a preceding charge-density wave (CDW) order that survives to temperatures well above the superconducting critical temperature, Tc. Whether the PDW is the mother or a subordinate order remains unsettled. Here, based on a systematic search for bulk charge order above Tc using resonant elastic X-ray scattering (REXS), we show that the structure factor of charge order previously identified by STM is absent in the bulk within the sensitivity of REXS. Our results invite two scenarios: either the density-wave orders condense simultaneously at Tc in the bulk, in which case PDW order is likely the mother phase, or the charge modulations are restricted to the surface.

Highly Selective On-Surface Dehydrogenative Aromatization of n-Hexyl to Phenyl Substituents.

Dehydrogenative aromatization of alkyl substituents represents a powerful approach to aryl-substituted functional molecules. However, the inertness of alkyl groups and the need for harsh reaction conditions accompanied by low product selectivity hamper its widespread applications. Here, we demonstrate the highly selective on-surface thermal aromatization of n-hexyl substituents on polycyclic aromatic hydrocarbons (PAHs) to their phenyl-substituted analogues under mild conditions. After depositing two representative precursor molecules, n-hexyl-substituted hexaphenylbenzene (HPB-Hex) and bianthryl octacarboxylic tetraimide (BATI-Hex), onto a pre-heated Au(111) substrate, dehydroaromatization of the peripheral n-hexyl groups into phenyl rings occurs, following the planarization of hexaphenylbenzene and bianthryl core. This process involves sequential intramolecular C-C bond rotations, dehydrogenation, and cyclodehydrogenation reactions, yielding phenyl-substituted hexabenzocoronene (HBC-Ph) and bisanthene octacarboxylic tetraimides (BSTI-Ph). The reaction sequences were monitored using scanning tunneling microscopy (STM) and bond-resolved non-contact atomic force microscopy (nc-AFM), offering structural proof of both intermediates and final products. These experimental techniques were complemented by density functional theory (DFT) simulations, which facilitated the detection of crucial steps in the conversion of n-hexyl to phenyl groups. Moreover, the effect of alkyl aromatization on the electronic properties of the newly formed aromatic hydrocarbons was elucidated using scanning tunneling spectroscopy (STS).

Two-Level Electronic Switching in Individual Manganese-Phthalocyanine Molecules with Jahn-Teller Distortion.

Understanding single molecular switches is a crucial step in designing and optimizing molecular electronic devices with highly nonlinear functionalities, e.g., gate voltage-dependent current switching. An atomically thin insulating template, in combination with scanning probe techniques, is an ideal platform to study such switches on the single-molecule level. In this study, we investigate manganese-phthalocyanine (MnPc) molecules on monolayer-thin epitaxial hexagonal boron nitride (h-BN) on Rh(111) by scanning tunneling microscopy (STM), spectroscopy (STS), and theoretical calculations. Several interesting phenomena are found: (1) high-resolution STM imaging of the molecular orbitals reveals symmetry breaking from D4h to D2h, observed in one type of MnPc. By comparison with simulations, this phenomenon can be attributed to the Jahn-Teller effect due to the negative charging of the molecule. (2) Ambipolar transitions at the molecule occur at fixed sample biases of about ±0.4 V, which manifest as negative differential conductance signatures in dI/dV spectroscopy. (3) The stochastic two-level switching, resulting in telegraphic noise in the tunneling current, manifests as a one-electron activated process. We present a two-level switching model to accurately describe a bias-dependent current-driven transition between the levels and reveal a first-order transition. The understanding and tailoring of molecular switches on the ultrathin insulating layer will be very helpful for future organic electronics design and application.

Scalable bottom-up synthesis of Co-Ni-doped graphene.

Introducing heteroatoms into graphene is a powerful strategy to modulate its catalytic, electronic, and magnetic properties. At variance with the cases of nitrogen (N)- and boron (B)-doped graphene, a scalable method for incorporating transition metal atoms in the carbon (C) mesh is currently lacking, limiting the applicative interest of model system studies. This work presents a during-growth synthesis enabling the incorporation of cobalt (Co) alongside nickel (Ni) atoms in graphene on a Ni(111) substrate. Single atoms are covalently stabilized within graphene double vacancies, with a Co load ranging from 0.07 to 0.22% relative to C atoms, controllable by synthesis parameters. Structural characterization involves variable-temperature scanning tunneling microscopy and ab initio calculations. The Co- and Ni-codoped layer is transferred onto a transmission electron microscopy grid, confirming stability through scanning transmission electron microscopy and electron energy loss spectroscopy. This method holds promise for applications in spintronics, gas sensing, electrochemistry and catalysis, and potential extension to graphene incorporation of similar metals.

Revealing the Microscopic Mechanism of Elementary Vortex Pinning in Superconductors

Vortex pinning is a crucial factor that determines the critical current of practical superconductors and enables their diverse applications. However, the underlying mechanism of vortex pinning has long been elusive, lacking a clear microscopic explanation. Here, using high-resolution scanning tunneling microscopy, we studied single vortex pinning induced by point defect in layered FeSe-based superconductors. We found the defect-vortex interaction drives low-energy vortex bound states away from EF, creating a “mini” gap that effectively lowers the system energy and enhances pinning. By measuring the local density of states, we directly obtained the elementary pinning energy and estimated the pinning force via the spatial gradient of pinning energy. The results are consistent with bulk critical current measurement. Furthermore, we showed that a general microscopic quantum model incorporating defect-vortex interaction can naturally capture our observation. It suggests that the local pairing near pinned vortex core is actually enhanced compared to unpinned vortex, which is beyond the traditional understanding that nonsuperconducting regions pin vortices. Our study thus unveils a general microscopic mechanism of vortex pinning in superconductors and provides insights for enhancing the critical current of practical superconductors. Published by the American Physical Society 2024

Single‐Molecule Mechanoresistivity by Intermetallic Bonding

AbstractThe metal‐electrode interface is key to unlocking emergent behaviour in all organic electrified systems, from battery technology to molecular electronics. In the latter, interfacial engineering has enabled efficient transport, higher device stability, and novel functionality. Mechanoresistivity – the change in electrical behaviour in response to a mechanical stimulus and a pathway to extremely sensitive force sensors – is amongst the most studied phenomena in molecular electronics, and the molecule‐electrode interface plays a pivotal role in its emergence, reproducibility, and magnitude. In this contribution, we show that organometallic molecular wires incorporating a Pt(II) cation show mechanoresistive behaviour of exceptional magnitude, with conductance modulations of more than three orders of magnitude upon compression by as little as 1 nm. We synthesised series of cyclometalated Pt(II) molecular wires, and used scanning tunnelling microscopy – break junction techniques to characterise their electromechanical behaviour. Mechanoresistivity arises from an interaction between the Pt(II) cation and the Au electrode triggered by mechanical compression of the single‐molecule device, and theoretical modelling confirms this hypothesis. Our study provides a new tool for the design of functional molecular wires by exploiting previously unreported ion‐metal interactions in single‐molecule devices, and develops a new framework for the development of mechanoresistive molecular junctions.

Mechanisms for the Spin-State Switching of Strapped Ni-Porphyrin Complexes Deposited on Metal Surfaces: Insights from Quantum Chemical Calculations.

The incorporation of molecular switches on nanodevices requires both the intactness of the molecule once deposited on a substrate and the persistence of the reversible switching feature. Recently, the reversible spin-switching of strapped Ni(II)-porphyrin complexes deposited on Ag(111) surface is demonstrated with low-temperature scanning tunneling microscopy (STM). The spin transition is accompanied by the coordination change of the metal center, a phenomenon denominated in coordination-induced spin-state switching (CISSS). In this contribution, the spin switching of the deposited strapped Ni-porphyrin molecules using different quantum chemistry approaches is explored. This calculations inform about the geometry and electronic structure of the adsorbed molecules and the origin of the voltage-dependent switching promoted by the STM tip. Two different mechanisms are inspected to elucidate the key role of the tip, mainly the electron injection between the tip and the molecule and the differential stabilization of the two spin states by the applied electric field between the tip and the silver surface. This study puts in evidence the relevance of the pyridine ligand contained in the strap in the transport properties as in the CISSS process itself.