Scanning Tunneling Spectroscopy Research Articles

Altering Spin Distribution of Tb2Pc3 via Molecular Chirality Manipulation.

Manipulating the chirality of the spin-polarized electronic state is pivotal for understanding many unusual quantum spin phenomena, but it has not been achieved at the single-molecule level. Here, using scanning tunneling microscopy and spectroscopy (STM/STS), we successfully manipulate the chirality of spin distribution in a triple-decker single-molecule magnet tris(phthalocyaninato)bis(terbium(III)) (Tb2Pc3), which is evaporated on a Pb(111) substrate via molecular beam epitaxy. The otherwise achiral Tb2Pc3 becomes chiral after being embedded into the self-assembled monolayer films of bis(phthalocyaninato)terbium(III) (TbPc2). The chirality of the spin distribution in Tb2Pc3 is manifested via the spatial mapping of its Kondo resonance state from its ligand orbital. Our first-principles calculations revealed that the spin and molecular chirality are associated with a small rotation followed by a structural distortion of the top Pc, consistent with the experimental observation. By constructing tailored molecular clusters with the STM tip, a single Tb2Pc3 molecule can be manipulated among achiral and differently handed chiral configurations of spin distributions reversibly. This paves the way for designing chiral spin enantiomers for fundamental studies and developing functional spintronic devices.

Revealing the temperature-driven Lifshitz transition in p-type Mg3Sb2-based thermoelectric materials

The manipulation of native atomic defects and their thermal excitations plays vital roles in the thermoelectric performance of Mg3Sb2-based materials. While native defects manipulation has been intensively studied in p-type Mg3Sb2, there exists interesting unsolved issue regarding the abnormal semiconducting electrical behavior in most of samples. In this work, high quality Mg3Sb2 and Mg3Bi2 (00l) films are fabricated by molecular beam epitaxy technique, while variable temperature angle-resolved photoemission spectroscopy and scanning tunneling spectroscopy measurements are utilized for resolving the aforementioned issue. The thermal excitation of Mg interstitials (the electron donor) results in an obvious downshift of valence bands with rising temperature in both the p-type Mg3Sb2 and Mg3Bi2. Meanwhile, the interesting temperature-driven Lifshitz transition is discovered in the p-type Mg3Sb2, as indicated by the change of Fermi surface topology. Above the Lifshitz transition temperature, the Fermi level of p-type Mg3Sb2 will enter the bandgap, which leads to the abnormal semiconducting electrical behavior. This work discloses the excitation of native defects and temperature-driven Lifshitz transition, which are the main causes for the anomalies in electrical transport of p-type Mg3Sb2-based materials, and also provides valuable insights for further improving their thermoelectric performance.

On-Surface Synthesis of Non-Benzenoid Nanographenes Embedding Azulene and Stone-Wales Topologies.

The incorporation of non-benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon-based electronics. However, understanding how specific non-benzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on-surface synthetic strategy toward fabricating non-benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa-a embeds two azulene units formed through oxidative ring-closure of methyl substituents, while Aa-s contains one azulene unit and one Stone-Wales defect, formed by the combination of oxidative ring-closure and skeletal ring-rearrangement reactions. Aa-a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non-benzenoid containing nanographene, coexisting with side-products with closed shell configurations resulted from the combination of ring-closure and ring-rearragement reactions (Ba-a , Ba-s , Bs-a and Bs-s ). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing non-benzenoid motifs and their tailored electronic/magnetic properties.

On‐Surface Synthesis of Non‐Benzenoid Nanographenes Embedding Azulene and Stone‐Wales Topologies

AbstractThe incorporation of non‐benzenoid motifs in graphene nanostructures significantly impacts their properties, making them attractive for applications in carbon‐based electronics. However, understanding how specific non‐benzenoid structures influence their properties remains limited, and further investigations are needed to fully comprehend their implications. Here, we report an on‐surface synthetic strategy toward fabricating non‐benzenoid nanographenes containing different combinations of pentagonal and heptagonal rings. Their structure and electronic properties were investigated via scanning tunneling microscopy and spectroscopy, complemented by computational investigations. After thermal activation of the precursor P on the Au(111) surface, we detected two major nanographene products. Nanographene Aa−a embeds two azulene units formed through oxidative ring‐closure of methyl substituents, while Aa−s contains one azulene unit and one Stone‐Wales defect, formed by the combination of oxidative ring‐closure and skeletal ring‐rearrangement reactions. Aa−a exhibits an antiferromagnetic ground state with the highest magnetic exchange coupling reported up to date for a non‐benzenoid containing nanographene, coexisting with side‐products with closed shell configurations resulted from the combination of ring‐closure and ring‐rearragement reactions (Ba−a, Ba−s, Bs‐a and Bs−s). Our results provide insights into the single gold atom assisted synthesis of novel NGs containing non‐benzenoid motifs and their tailored electronic/magnetic properties.

2D Lateral Heterojunction Arrays with Tailored Interface Band Bending.

Two-dimensional (2D) lateral heterojunction arrays, characterized by well-defined electronic interfaces, hold significant promise for advancing next-generation electronic devices. Despite this potential, the efficient synthesis of high-density lateral heterojunctions with tunable interfacial band alignment remains a challenging. Here, a novel strategy is reported for the fabrication of lateral heterojunction arrays between monolayer Si2Te2 grown on Sb2Te3 (ML-Si2Te2@Sb2Te3) and one-quintuple-layer Sb2Te3 grown on monolayer Si2Te2 (1QL-Sb2Te3@ML-Si2Te2) on a p-doped Sb2Te3 substrate. The site-specific formation of numerous periodically arranged 2D ML-Si2Te2@Sb2Te3/1QL-Sb2Te3@ML-Si2Te2 lateral heterojunctions is realized solely through three epitaxial growth steps of thick-Sb2Te3, ML-Si2Te2, and 1QL-Sb2Te3 films, sequentially. More importantly, the precisely engineering of the interfacial band alignment is realized, by manipulating the substrate's p-doping effect with lateral spatial dependency, on each ML-Si2Te2@Sb2Te3/1QL-Sb2Te3@ML-Si2Te2 junction. Atomically sharp interfaces of the junctions with continuous lattices are observed by scanning tunneling microscopy. Scanning tunneling spectroscopy measurements directly reveal the tailored type-II band bending at the interface. This reported strategy opens avenues for advancing lateral epitaxy technology, facilitating practical applications of 2D in-plane heterojunctions.

Asymmetric Molecular Adsorption and Regioselective Bond Cleavage on Chiral PdGa Crystals.

Homogenous enantioselective catalysis is nowadays the cornerstone in the manufacturing of enantiopure substances, but its technological implementation suffers from well-known impediments like the lack of endurable catalysts exhibiting long-term stability. The catalytically active intermetallic compound Palladium-Gallium (PdGa), conserving innate bulk chirality on its surfaces, represent a promising system to study asymmetric chemical reactions by heterogeneous catalysis, with prospective relevance for industrial processes. Here, this work investigates the adsorption of 10,10'-dibromo-9,9'-bianthracene (DBBA) on the PdGa:A( ) Pd3-terminated surface by means of scanning tunneling microscopy (STM) and spectroscopy (STS). A highly enantioselective adsorption of the molecule evolving into a near 100% enantiomeric excess below room temperature is observed. This exceptionally high enantiomeric excess is attributed to temperature activated conversion of the S to the R chiral conformer. Tip-induced bond cleavage of the R conformer shows a very high regioselectivity of the DBBA debromination. The experimental results are interpreted by density functional theory atomistic simulations. This work extends the knowledge of chirality transfer onto the enantioselective adsorption of non-planar molecules and manifests the ensemble effect of PdGa surfaces resulting in robust regioselective debromination.

Variation in the Bandgap of Amorphous Zinc Tin Oxide: Investigating the Thickness Dependence via In Situ STS.

Amorphous transparent conducting oxides (a-TCOs) have seen substantial interest in recent years due to the significant benefits that they can bring to transparent electronic devices. One such material of promise is amorphous ZnxSn1-xOy (a-ZTO). a-ZTO possesses many attractive properties for a TCO such as high transparency in the visible range, tunable charge carrier concentration, electron mobility, and only being composed of common and abundant elements. In this work, we employ a combination of UV-vis spectrophotometry, X-ray photoemission spectroscopy, and in situ scanning tunneling spectroscopy to investigate a 0.33 eV blue shift in the optical bandgap of a-ZTO, which we conclude to be due to quantum confinement effects.

The topological soliton in Peierls semimetal Sb

Sb is a three-dimensional Peierls insulator. The Peierls instability gives rise to doubling of the translational period along the [111] direction and alternating van der Waals and covalent bonding between (111) atomic planes. At the (111) surface of Sb, the Peierls condition is violated, which in theory can give rise to properties differing from the bulk. The atomic and electronic structure of the (111) surface of Sb have been simulated by density functional theory calculations. We have considered the two possible (111) surfaces, containing van der Waals dangling bonds or containing covalent dangling bonds. In the models, the surfaces are infinite and the structure is defect free. Structural optimization of the model containing covalent dangling bonds results in strong deformation, which is well described by a topological soliton within the Su–Schrieffer–Heeger model centered about 25 Å below the surface. The electronic states associated with the soliton see an increase in the density of states (DOS) at the Fermi level by around an order of magnitude at the soliton center. Scanning tunneling microscopy and spectroscopy (STM/STS) measurements reveal two distinct surface regions, indicating that there are different surface regions cleaving van der Waals and covalent bonds. The DFT is in good agreement with the STM/STS experiments.

On-surface synthesis and characterization of polyynic carbon chains.

Carbyne, an elusive sp-hybridized linear carbon allotrope, has fascinated chemists and physicists for decades. Due to its high chemical reactivity and extreme instability, carbyne was much less explored in contrast to the sp2-hybridized carbon allotropes such as graphene. Herein, we report the on-surface synthesis of polyynic carbon chains by demetallization of organometallic polyynes on the Au(111) surface; the longest one observed consists of ∼60 alkyne units (120 carbon atoms). The polyynic structure of carbon chains with alternating triple and single bonds was unambiguously revealed by bond-resolved atomic force microscopy. Moreover, an atomically precise polyyne, C14, was successfully produced via tip-induced dehalogenation and ring-opening of the decachloroanthracene molecule (C14Cl10) on a bilayer NaCl/Au(111) surface at 4.7K, and a band gap of 5.8eV was measured by scanning tunnelling spectroscopy, in a good agreement with the theoretical HOMO-LUMO gap (5.48eV).

Unconventional Charge-Density-Wave Gap in Monolayer NbS2.

Using scanning tunneling microscopy and spectroscopy, for a monolayer of transition metal dichalcogenide H-NbS2 grown by molecular beam epitaxy on graphene, we provide unambiguous evidence for a charge density wave (CDW) with a 3 × 3 superstructure, which is not present in bulk NbS2. Local spectroscopy displays a pronounced gap on the order of 20 meV at the Fermi level. Within the gap, low-energy features are present. The gap structure with its low-energy features is at variance with the expectation for a gap opening in the electronic band structure due to a CDW. Instead, comparison with ab initio calculations indicates that the observed gap structure must be attributed to combined electron-phonon quasiparticles. The phonons in question are the elusive amplitude and phase collective modes of the CDW transition. Our findings advance the understanding of CDW mechanisms in 2D materials and their spectroscopic signatures.

Tuning commensurability in twisted van der Waals bilayers.

Moiré superlattices based on van der Waals bilayers1-4 created at small twist angles lead to a long wavelength pattern with approximate translational symmetry. At large twist angles (θt), moiré patterns are, in general, incommensurate except for a few discrete angles. Here we show that large-angle twisted bilayers offer distinctly different platforms. More specifically, by using twisted tungsten diselenide bilayers, we create the incommensurate dodecagon quasicrystals at θt = 30° and the commensurate moiré crystals at θt = 21.8° and 38.2°. Valley-resolved scanning tunnelling spectroscopy shows disparate behaviours between moiré crystals (with translational symmetry) and quasicrystals (with broken translational symmetry). In particular, the Kvalley shows rich electronic structures exemplified by the formation of mini-gaps near the valence band maximum. These discoveries demonstrate that bilayers with large twist angles offer a design platform to explore moiré physics beyond those formed with small twist angles.

Modulation of Carbon Nanotube Electronic Structure by Grain Boundary Defects in RbI on Au(111).

The electronic properties of single-walled carbon nanotubes (SWCNTs) are known to be highly sensitive to environmental effects. Here, we use scanning tunneling microscopy and spectroscopy to investigate the electronic properties of SWCNTs deposited on RbI monolayer films grown on Au(111). We find that grain boundary defects in RbI monolayers cause the appearance of spatially confined localized states in the SWCNTs. Our density functional theory calculations show that grain boundary defects in RbI/Au(111) produce a stabilizing electrostatic potential caused by reduced coordination of iodine atoms at the RbI grain boundary. The presented results may offer insights into the performance of devices involving transport through SWCNTs subjected to external electrostatic disorder.

ARPES investigation of the electronic structure and its evolution in magnetic topological insulator MnBi2+2nTe4+3n family.

In the past 5 years, there has been significant research interest in the intrinsic magnetic topological insulator family compounds MnBi2+2nTe4+3n (where n=0, 1, 2 …). In particular, exfoliated thin films of MnBi2Te4 have led to numerous experimental breakthroughs, such as the quantum anomalous Hall effect, axion insulator phase and high-Chern number quantum Hall effect without Landau levels. However, despite extensive efforts, the energy gap of the topological surface states due to exchange magnetic coupling, which is a key feature of the characteristic band structure of the system, remains experimentally elusive. The electronic structure measured by using angle-resolved photoemission (ARPES) shows significant deviation from ab initio prediction and scanning tunneling spectroscopy measurements, making it challenging to understand the transport results based on the electronic structure. This paper reviews the measurements of the band structure of MnBi2+2nTe4+3n magnetic topological insulators using ARPES, focusing on the evolution of their electronic structures with temperature, surface and bulk doping and film thickness. The aim of the review is to construct a unified picture of the electronic structure of MnBi2+2nTe4+3n compounds and explore possible control of their topological properties.

Imaging moiré excited states with photocurrent tunnelling microscopy.

Moiré superlattices provide a highly tuneable and versatile platform to explore novel quantum phases and exotic excited states ranging from correlated insulators to moiré excitons. Scanning tunnelling microscopy has played a key role in probing microscopic behaviours of the moiré correlated ground states at the atomic scale. However, imaging of quantum excited states in moiré heterostructures remains an outstanding challenge. Here we develop a photocurrent tunnelling microscopy technique that combines laser excitation and scanning tunnelling spectroscopy to directly visualize the electron and hole distribution within the photoexcited moiré exciton in twisted bilayer WS2. The tunnelling photocurrent alternates between positive and negative polarities at different locations within a single moiré unit cell. This alternating photocurrent originates from the in-plane charge transfer moiré exciton in twisted bilayer WS2, predicted by our GW-Bethe-Salpeter equation calculations, that emerges from the competition between the electron-hole Coulomb interaction and the moiré potential landscape. Our technique enables the exploration of photoexcited non-equilibrium moiré phenomena at the atomic scale.

Evidence of thickness-dependent surface-induced ferroelectricity in few-layer germanium sulfide obtained via scanning tunneling spectroscopy.

The discovery of ferroelectricity in two-dimensional van der Waals materials has sparked enormous interest from the scientific community, due to its possible applications in next-generation nanoelectronic devices, such as random-access memory devices, digital signal processors, and solar cells, among others. In the present study, we used vapor phase deposition to synthesize ultrathin germanium sulfide nano-flakes on a highly oriented pyrolytic graphite substrate. Nanostructures of variable thicknesses were characterized using scanning tunneling microscopy and spectroscopy. Tunneling currents under forward and backward biases were measured as a function of nano-flake thickness. Remarkably, we clearly observed a hysteresis pattern, which we attributed to surface ferroelectric behavior, consistent with the screening conditions of polarization charges. The effect increases as the number of layers is reduced. This experimental result may be directly applicable to miniaturized memory devices, given the two-dimensional nature of this effect.

Thermally-induced nanoscale phase change in chalcogenide glass Cr2Ge2Te6 revealed by scanning tunneling microscopy

Cr2Ge2Te6 (CrGT) is viewed as an important phase change material (PCM) for next-generation nonvolatile memory devices because of its superior properties, e.g., high thermal stability and low operation energy, compared to conventional PCMs. However, the phase change mechanism of CrGT remains unsolved, especially at the nanoscale. Here, we investigated thermally induced nanoscale phase changes of CrGT thin films using scanning tunneling microscopy (STM) and scanning tunneling spectroscopy (STS). By performing statistical analysis of the measured STM topographic and STS data, we evaluated the inhomogeneity and distribution of the phase change characteristics of CrGT thin films. We also related the nanoscale phase change properties of CrGT to macroscopic phase changes by comparing the STM and STS results with experimental data from Raman spectroscopy.

Exploring the characteristic "plug-in" configuration of an adsorbed starburst molecule.

In this study, the adsorption of starburst molecules (C57H48N4, SBM) deposited on Au(111) was investigated by scanning tunneling microscopy (STM). SBM molecules selectively adsorb on the face-centered-cubic regions of Au(111) in quasi one-dimensional chains. Compared with the SBM structure on hBN/Rh(111), the assembly structure of SBM on Au(111) can be clearly confirmed to be molecular chains in the "plug-in" configuration. Scanning tunneling spectroscopy (STS) revealed that the interaction between SBM molecules and Au(111) induces the modification of the molecular electronic states. The STS mapping further revealed a continuous 1D electronic state concentrated at the center of the SBM molecular chains.

On surface synthesis of an eleven-ring sulfur-doped nonacene.

Dithienoacenes with a heptacene core, heptaceno[2,3-b:11,12-b']bis[1]benzothiophene, have been synthesized through the combination of solution and surface assisted chemistry. The atomic composition, structural arrangement and electronic properties of the molecules on the Au(111) surface have been deeply explored by non-contact atomic force microscopy (nc-AFM), bond-resolved scanning tunnelling microscopy (BR-STM) and scanning tunneling spectroscopy (STS) corroborated by density functional theory (DFT) calculations. Our combined experiments reveal modifications induced by sulfur substitution.

Spontaneous switching and fine structure of donor-acceptor Stenhouse adducts on Au(111).

We present the spontaneous isomerization of donor-acceptor Stenhouse adducts anchored onto a gold surface, visualized using scanning tunneling spectroscopy. Our investigation reveals a palette of molecular arrangements, including those with ferroelectric-like ordering, evolving over time into a fine pattern consisting of both open and closed forms of the photoswitch.

An approach for patterned molecular adsorption on ferromagnets, achieved via Moiré superstructures.

We have used a scanning tunneling microscope operated under ultrahigh vacuum conditions to investigate an oxo-vanadium-salen complex V(O)salen, that has potential applications as qubits in future quantum-based technologies. The adsorption and self-assembly of V(O)salen on a range of single crystal metal surfaces and nanoislands and the influence of substrate morphology and reactivity has been measured. On the close-packed flat Ag(111) and Cu(111) surfaces, the molecules adsorb isolated or form small clusters arranged randomly on the surface, whereas structured adsorption occurs on two types of Co nanoislands; Co grown on Ag(111) and Ag capped Co islands grown on Cu(111), both forming a Moiré pattern at the surface. The adsorption configuration can by scanning tunneling spectroscopy be linked to the geometric and electronic properties of the substrates and traced back to a Co d-related surface state, illustrating how the modulated reactivity can be used to engineer a pattern of adsorbed molecules on the nanoscale.