Scanning Tunneling Research Articles

Double-pentagon silicon chains in a quasi-1D Si/Ag(001) surface alloy

Silicon surface alloys and silicide nanolayers are highly important as contact materials in integrated circuit devices. Here we demonstrate that the submonolayer Si/Ag(001) surface reconstruction, reported to exhibit interesting topological properties, comprises a quasi-one-dimensional Si-Ag surface alloy based on chains of planar double-pentagon Si moieties. This geometry is determined using a combination of density functional theory calculations, scanning tunnelling microscopy, and grazing incidence x-ray diffraction simulations, and yields an electronic structure in excellent agreement with photoemission measurements. This work provides further evidence of pentagonal geometries in 2D materials and heterostructures and elucidates the importance of surface alloying in stabilizing their formation.

Charge-transfer dipole low-frequency vibronic excitation at single-molecular scale.

Scanning tunneling microscopy (STM) vibronic spectroscopy, which has provided submolecular insights into electron-vibration (vibronic) coupling, faces challenges when probing the pivotal low-frequency vibronic excitations. Because of eigenstate broadening on solid substrates, resolving low-frequency vibronic states demands strong decoupling. This work designs a type II band alignment in STM junction to achieve effective charge-transfer state decoupling. This strategy enables the successful identification of the lowest-frequency Hg(ω1) (Raman-active Hg mode) vibronic excitation within single C60 molecules, which, despite being notably pronounced in electron transport of C60 single-molecule transistors, has remained hidden at submolecular level. Our results show that the observed Hg(ω1) excitation is "anchored" to all molecules, irrespective of local geometry, challenging common understanding of structural definition of vibronic excitation governed by Franck-Condon principle. Density functional theory calculations reveal existence of molecule-substrate interfacial charge-transfer dipole, which, although overlooked previously, drives the dominant Hg(ω1) excitation. This charge-transfer dipole is not specific but must be general at interfaces, influencing vibronic coupling in charge transport.

Unearthing Atomic Dynamics in Nanocatalysts.

Being able to access the rich atomic-scale phenomenology, which occurs during the reactions pathways, is a pressing need toward the pursued knowledge-based design of more efficient nanocatalysts, precisely tailored atom by atom for each reaction. However, to reach this goal of achieving maximum optimization, it is mandatory, first, to address how exposure to the experimental conditions, which will be needed to activate the processes, affects the internal configuration of the nanoparticles at the atomic level. In particular, the most critical experimental parameter is probably the temperature, which among other unwanted effects can induce nanocatalyst aggregation. This work highlights the high potential of experimental techniques such as the scanning probe microscopies, which are able to investigate matter in real space with atomic resolution, to reach the key challenge in heterogeneous catalysis of achieving access to the atomic-scale processes taking place in the nanocatalysts. Specifically, the phenomenology occurring in a nanoparticle system during annealing is studied with atomic precision by scanning tunneling microscopy. As a result, the existence of an internal atomic restructuring, occurring already at relatively low temperatures, within Ir nanoparticles grown over h-BN/Ru(0001) surfaces is demonstrated. Such restructuration, which reduces the undercoordination of the outer Ir atoms, is expected to have a significant effect on the reactivity of the nanoparticles. Going a step further, an internal restructuring of the nanoparticles during their involvement as catalysts has also been also identified.

Topological Band Engineering of One-Dimensional π-d Conjugated Metal-Organic Frameworks.

One-dimensional (1D) π-d conjugated metal-organic frameworks (c-MOFs) have garnered widespread research interest in chemical energy storage and conversion. In this work, we introduce a universal principle to engineer the topological bands of 1D c-MOFs. Connected by d orbitals of transition metals, two equivalent hidden molecular π orbitals in 1D c-MOFs can generate a staggered hopping within and between the organic ligands, forming Su-Schrieffer-Heeger-shaped 1D topological bands. Guided by this discovery, we investigate the electronic structures of the typical 1D c-MOF assembled from Ni atoms and 2HQDI (QDI = 2,5-diamino-1,4-benzoquinonediimine) precursors (NiQDI) by first-principles calculations, revealing 1D topological bands around the Fermi level. Due to local bonding variations at the QDI terminations, these two hidden molecular π orbitals become atomically bonded but electronically separated at the edge QDI, creating spatially localized in-gap topological edge states at the end of the NiQDI chain. This definitive signature for 1D topological bands is identified through differential conductance spectra in scanning tunneling microscopy measurements. Our results provide conclusive experimental evidence for topological bands in 1D c-MOFs, paving the way for exploring the topological physics in organic materials through frontier molecular orbitals.

Proximity-Induced Superconductivity in a 2D Kondo Lattice of an f-Electron-Based Surface Alloy.

Realizing hybrids of low-dimensional Kondo lattices and superconducting substrates leads to fascinating platforms for studying the exciting physics of strongly correlated electron systems with induced superconducting pairing. Here, we report a scanning tunneling microscopy and spectroscopy study of a new type of two-dimensional (2D) La-Ce alloy grown epitaxially on a superconducting Re(0001) substrate. We observe the characteristic spectroscopic signature of a hybridization gap evidencing the coherent spin screening in the 2D Kondo lattice realized by the ultrathin La-Ce alloy film on normal conducting Re(0001). Upon lowering the temperature below the critical temperature of rhenium, a superconducting gap is induced exhibiting an energy asymmetry of the coherence peaks that arises from the interaction of residual unscreened magnetic moments with the superconducting substrate. A positive correlation between the Kondo hybridization gap and the asymmetry of the coherence peaks is found.

Imaging Quantum Interference in a Monolayer Kitaev Quantum Spin Liquid Candidate

Single atomic defects are prominent windows to look into host quantum states because collective responses from the host states emerge as localized states around the defects. Friedel oscillations and Kondo clouds in Fermi liquids are quintessential examples. However, the situation is quite different for quantum spin liquid (QSL), an exotic state of matter with fractionalized quasiparticles and topological order arising from a profound impact of quantum entanglement. Elucidating the underlying local electronic property has been challenging due to the charge neutrality of fractionalized quasiparticles and the insulating nature of QSLs. Here, using spectroscopic-imaging scanning tunneling microscopy, we report atomically resolved images of monolayer α−RuCl3, the most promising Kitaev QSL candidate, on metallic substrates. We find quantum interference in the insulator manifesting as incommensurate and decaying spatial oscillations of the local density of states around defects with a characteristic bias dependence. The oscillation differs from any known spatial structures in its nature and does not exist in other Mott insulators, implying it is an exotic oscillation involved with excitations unique to α−RuCl3. Numerical simulations suggest that the observed oscillation can be reproduced by assuming that itinerant Majorana fermions of Kitaev QSL are scattered across the Majorana Fermi surface. The oscillation provides a new approach to exploring Kitaev QSLs through the local response against defects like Friedel oscillations in metals. Published by the American Physical Society 2024

Manipulative Single Electric Dipole with Spontaneous Translational Symmetry Breaking in a Two-Dimensional Crystal.

It is widely acknowledged that quantum entities with minimal mass cannot undergo spontaneous symmetry breaking due to strong quantum fluctuations. Here, we report the discovery of a positionally settled single electric dipole that can be manipulated and electrically polarized in a monolayer CoCl2-graphite heterostructure, which demonstrates an unprecedented example of spontaneous lattice-translational-symmetry breaking. Scanning tunneling microscopy and atomic force microscopy show that the solitons are intrinsic paraelectric dipoles driven by synchronous charge-lattice distortion around individual CoCl6 octahedrons. Both the dipole moment and lateral position of the soliton can be manipulated by the electric field exerted from the tip, which offers polarity-switchable and layout-designable electrostatic potential landscapes that determine the band bending configuration. This study exemplifies a brand-new type of local charge-lattice order, appealing for further research on the mechanism underlying the soliton robustness, and the electrically and positionally controllable single dipole supports the feasibility of band tailoring in device applications.

Charged Impurity Scattering and Electron-Electron Interactions in Large-Area Hydrogen Intercalated Bilayer Graphene.

Intercalation is a promising technique to modify the structural and electronic properties of 2D materials on the wafer scale for future electronic device applications. Yet, few reports to date demonstrate 2D intercalation as a viable technique on this scale. Spurred by recent demonstrations of mm-scale sensors, we use hydrogen intercalated quasi-freestanding bilayer graphene (hQBG) grown on 6H-SiC(0001), to understand the electronic properties of a large-area (16 mm2) device. To do this, we first analyze Shubnikov-de Haas (SdH) oscillations and weak localization, permitting determination of the Fermi level, cyclotron effective mass, and quantum scattering time. Our transport results indicate that at low temperature, scattering in hQBG is dominated by charged impurities and electron-electron interactions. Using low- temperature scanning tunneling microscopy and spectroscopy (STS), we investigate the source of the charged impurities on the nm-scale via observation of Friedel oscillations. Comparison to theory suggests that the Friedel oscillations we observe are caused by hydrogen vacancies underneath the hQBG. Furthermore, STS measurements demonstrate that hydrogen vacancies in the hQBG have an extremely localized effect on the local density of states, such that the Fermi level of the hQBG is only affected directly above the location of the defect. Hence, we find that the calculated Fermi level from SdH oscillations on the millimeter scale agrees with the value measured locally on the nanometer scale with STS measurements.

Conductance Channels in a Single-Entity Enzyme.

For a long time, the prevailing view in the scientific community was that proteins, being complex macromolecules composed of amino acid chains linked by peptide bonds, adopt folded structure with insulating or semiconducting properties, with high bandgaps. However, recent discoveries of unexpectedly high conductance levels, reaching values in the range of dozens of nanosiemens (nS) in proteins, have challenged this conventional understanding. In this study, we used scanning tunneling microscopy (STM) to explore the single-entity conductance properties of enzymatic channels, focusing on bilirubin oxidase (BOD) as a model metalloprotein. By immobilizing BOD on a conductive carbon surface, we discern its preferred orientation, facilitating the formation of electronic and ionic channels. These channels show efficient electron transport (ETp), with apparent conductance up to the 15 nS range. Notably, these conductance pathways are localized, minimizing electron transport barriers due to solvents and ions, underscoring BOD's redox versatility. Furthermore, electron transfer (ET) within the BOD occurs via preferential pathways. The alignment of the conductance channels with hydrophilicity maps, molecular vacancies, and regions accessible to electrolytes explains the observed conductance values. Additionally, BOD exhibits redox activity, with its active center playing a critical role in the ETp process. These findings significantly advance our understanding of the intricate mechanisms that govern ETp processes in proteins, offering new insights into the conductance of metalloproteins.

Rapid Synthesis of Uniformly Small Nickel Nanoparticles for the Surface Functionalization of Epitaxial Graphene

AbstractNickel nanoparticles (Ni NPs) combined with carbon nanomaterials are of significant interest due to their wide range of applications, including catalysis, hydrogen storage, and sensor technologies. However, it is challenging to develop an efficient process to produce small and stable Ni NPs ideal for functionalizing graphene or substrates with complex geometries. For this purpose, a rapid, simple, and cost‐effective method is presented for synthesizing uniformly small Ni NPs. The process involves cooling aqueous solutions of Ni(OAc)2 and cetyltrimethylammonium bromide (CTAB) to ≈1 °C, followed by the rapid addition of NaBH4. Crucial parameters, such as temperature and stirring rate, are precisely controlled to ensure uniform particle growth, with the reaction completing in just a few minutes. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) characterizations reveal spherical NPs with an average diameter of ≈11 nm and a narrow size distribution. Additionally, epitaxial graphene (EG) samples are functionalized with the synthesized NPs and their arrangement on the surface and their stability upon thermal annealing are investigated. X‐ray photoelectron spectroscopy (XPS) and scanning tunneling microscopy (STM) measurements demonstrate the degradation of CTAB, along with the recovery of Ni(0) under mild conditions (below 350 °C), with the NPs maintaining structural stability up to approximately 550 °C.

Scalable Metal–Organic Chemical Vapor Deposition of High Quality PtSe2

AbstractPlatinum diselenide (PtSe2), a 2D noble metal dichalcogenide, has recently received significant attention due to its outstanding properties. It undergoes a semimetal to semiconductor transition when thinned, offers a bandgap in the infrared range, and exhibits excellent stability in ambient conditions. These properties make it a prime active material in optoelectronic and chemical sensing devices. However, there is a high demand for a synthesis method that can produce large‐scale and reliable high‐quality PtSe2. In this study, the growth of PtSe2 is presented by metal–organic vapor deposition on a variety of substrates. Comprehensive Raman, X‐ray photoelectron, and X‐ray diffraction spectroscopy, as well as scanning tunneling microscopy characterization reveals the high quality of the deposited PtSe2. Domains within the films are found to be up to several hundreds of nanometers in size, and their highly ordered crystalline structure is evident from atomic‐scale measurements. Electrical characterization demonstrates improved conductivity relative to conventional synthesis methods. This study provides fundamental guidance for the scalable synthesis and implementation of high quality PtSe2 layers with controllable thickness, offering a key requirement for the implementation of PtSe2 in future applications.

Harnessing Quantum Materials for Enhanced Energy Efficiency and Storage: A Comprehensive Study of Electronic Properties and Performance Optimization

This research explores the exciting potential of various quantum materials to enhance energy efficiency and storage capabilities, filling in a crucial gap in our understanding of their electronic properties and interactions. A major hurdle in this field is the lack of empirical data on key factors such as conductivity, charge mobility, and thermal stability—elements that are vital for optimizing the performance of these materials in energy applications. Our study aims to blend experimental data with computational simulations to create a robust framework for modelling how quantum materials behave under different conditions. This comprehensive approach helps lay a solid foundation for their practical use in energy technologies. We focus on an array of fascinating quantum materials, including topological insulators, transition metal dichalcogenides, and superconductors. To investigate these materials, we employ advanced techniques like scanning tunnelling microscopy and spectroscopy, which allow us to delve deep into their unique properties. While pursuing this research, we do encounter challenges. Variations in sample quality, environmental factors during experimentation, and the complexities of theoretical modelling can affect the consistency of our results and the interpretation of our data. Despite these obstacles, our findings suggest that certain quantum materials hold remarkable potential for enhancing energy storage and conversion systems through improved charge mobility and thermal stability. In fact, some materials have demonstrated conductivity levels that surpass those of traditional options, hinting at transformative applications in energy technologies. These insights highlight the importance of continuing our exploration of quantum materials, positioning them as promising candidates for tackling today’s energy challenges and paving the way for advancements in sustainable energy solutions.

Superconducting density of states and vortex lattice of LaRu2P2 observed by scanning tunneling spectroscopy

We provide the superconducting density of states of the pnictide superconductor LaRu2P2(Tc= 4.1 K), measured using millikelvin scanning tunneling microscopy. From the tunneling conductance, we extract a density of states which shows the opening of a s-wave single superconducting gap. The temperature dependence of the gap also follows BCS theory. Under magnetic fields, vortices present Caroli de Gennes Matricon states, although these are strongly broadened by defect scattering. From the vortex core size we obtain a superconducting coherence length ofξ = 50 nm, compatible with the value extracted from macroscopicHc2measurements. We discuss the comparison between s-wave LaRu2P2and pnictide unconventional multiple gap and strongly correlated Fe based superconductors.

Label-Free Single-Molecule Electrical Sensor for Ultrasensitive and Selective Detection of Iodide Ions in Human Urine.

Herein, a label-free single-molecule electrical sensor was first proposed for the ultrasensitive and selective detection of iodide ions in human urine. Single-molecule conductance measurements in different halogen ion solutions via scanning tunneling microscopy break junction (STM-BJ) clearly revealed that I- ions strongly affect the stability and displacement distance (Δz) distribution of molecular junctions. Theoretical calculations prove that the specific adsorption of I- ions modifies the surface properties and weakens the molecular adsorption. Furthermore, the average conductance peak area versus the logarithm of the I- ion concentration has a very good linear relationship in the range of 5 × 10-6 to 5 × 10-10 M, with a correlation coefficient of 0.99. This quantitative analysis remains valid in the presence of interfering ions of SO42-, ClO4-, Br-, and Cl- as well as interfering molecules of ascorbic acid, uric acid, dopamine, and cysteine. A cross-comparison of the human urine detection results of this single-molecule electrical sensor with those of the clinical method of As3+-Ce4+ catalytic spectrophotometry revealed an average difference of 0.9%, which decreased the detection time of 2 h with the traditional method to approximately 15 min. This work proves the promising practical potential of the single-molecule electrical technique for relevant clinical analysis.

Atomic structure of different surface terminations of polycrystalline ZnPd

The intermetallic compound ZnPd has been found to have desirable characteristics as a catalyst for the steam reforming of methanol. The understanding of the surface structure of ZnPd is important to optimize its catalytic behavior. However, due to the lack of bulk single-crystal samples and the complexity of characterizing surface properties in the available polycrystalline samples using common experimental techniques, all previous surface science studies of this compound have been performed on surface alloy samples formed through thin-film deposition. In this study, we present findings on the chemical and atomic structure of the surfaces of bulk polycrystalline ZnPd studied by a variety of complementary experimental techniques, including scanning tunneling microscopy (STM), x-ray photoelectron spectroscopy (XPS), low energy electron microscopy (LEEM), photoemission electron microscopy (PEEM), and microspot low-energy electron diffraction (μ-LEED). These experimental techniques, combined with density functional theory (DFT)-based thermodynamic calculations of surface free energy and detachment kinetics at the step edges, confirm that surfaces terminated by atomic layers composed of both Zn and Pd atoms are more stable than those terminated by only Zn or Pd layers. DFT calculations also demonstrate that the primary contribution to the tunneling current arises from Pd atoms, in agreement with the STM results. The formation of intermetallics at surfaces may contribute to the superior catalyst properties of ZnPd over Zn or Pd elemental counterparts. Published by the American Physical Society 2024

Atomically Precise Control of Topological State Hybridization in Conjugated Polymers.

Realization of topological quantum states in carbon nanostructures has recently emerged as a promising platform for hosting highly coherent and controllable quantum dot spin qubits. However, their adjustable manipulation remains elusive. Here, we report the atomically accurate control of the hybridization level of topologically protected quantum edge states emerging from topological interfaces in bottom-up-fabricated π-conjugated polymers. Our investigation employed a combination of low-temperature scanning tunneling microscopy and spectroscopy, along with high-resolution atomic force microscopy, to effectively modify the hybridization level of neighboring edge states by the selective dehydrogenation reaction of molecular units in a pentacene-based polymer and demonstrate their reversible character. Density functional theory, tight binding, and complete active space calculations for the Hubbard model were employed to support our findings, revealing that the extent of orbital overlap between the topological edge states can be finely tuned based on the geometry and electronic bandgap of the interconnecting region. These results demonstrate the utility of topological edge states as components for designing complex quantum arrangements for advanced electronic devices.

Advancing Graphene Imaging for Clear Identification of Lattice Defects: The Application of Revolve Sphere Levelling to Scanning Tunnelling Microscopy Images.

Application of revolve sphere levelling (RSL) as a practical and effective image processing tool for enhancing scanning tunnelling microscopy (STM) images of graphene atomic lattices is presented. Low-cost, ambient, and non-invasive STM methods overcome limitations of traditional imaging methods like scanning transmission electron microscopy (STEM) and transmission electron microscopy (TEM) that can introduce or alter defects in graphene. Utilizing high-quality graphene synthesized via Paragraf's patented Metal-Organic Chemical Vapor Deposition (MOCVD) method, RSL, which is easily implemented via the Gwyddion software package, effectively highlights the hexagonal lattice structure and specific defect structures. This provides clarity of the atomic structure that traditional methods struggle to achieve. This research emphasizes the utility of RSL in materials science for defect identification in graphene, and points to future research in optimizing RSL for a broader range of defects and applications in other 2D materials.

Quasi-one-dimensional bismuth chains with topological properties

One-dimensional (1D) systems have received a lot of attention due to their exotic physical phenomena such as quantization of conductance, Peierls instability, and Luttinger liquid behavior. Here, we present the synthesis of self-assembled quasi-1D bismuth (Bi) chains on an Au(111) substrate, highlighting their topological properties. Scanning tunneling microscopy and spectroscopy measurements reveal that the high-quality large area array is composed of Bi atomic chains with a bandgap of 0.5 eV. Density functional theory (DFT) calculations confirm the experimental observation and reveal the topological properties of the system, providing evidence of the spin texture of the Bi atomic chains. Our DFT results predict that a single Bi chain hosts exotic topological properties. The atomically precise synthesis of Bi atomic chains overcomes the limitation of the top-down approach toward integration of devices. The work sheds light on the realization of 1D system, providing a platform for further investigation into the intriguing physics in 1D systems.

Lying or Standing of Thiophene on a Surface Determines the Reaction Difference.

Adsorption configurations of molecules on a surface play an important role in the on-surface reaction. In the on-surface synthesis reaction, most of the molecules prefer the lying adsorption configuration to maximize the interaction between the molecule and substrate. In this work, we report an on-surface study of 2,3,4,5-tetrabromothiophene by scanning tunneling microscopy, density functional theory, and X-ray photoelectron spectroscopy. Due to different interactions between thiophene and metal surfaces, lying or standing configurations of 2,3,4,5-tetrabromothiophene can be selected by the choice of metal substrates. Moreover, a catalytic role of the metal substrate in the molecular reaction with lying and standing adsorption configurations is demonstrated at the molecular level. This work broadens the understanding of thiophene's configurations in surface reactions and the product diversity driven by adsorption configurations. It also offers a guiding framework for synthesizing multifunctional materials by thiophene derivatives.

Probing Surface-Mediated Electronic Coupling in Flat Hexagonal Phosphorus Nanostructures and Monolayer on Au(111).

Due to its diverse allotropes and intriguing properties, 2D phosphorus, also known as phosphorene, is a material of great interest. Here, the successful growth of flat hexagonal 2D phosphorus on Au(111) is reported. Starting from phosphorus linear chains at low coverage, a porous network and finally an extended 2D flat hexagonal (HexP) layer while increasing phosphorus deposition is formed. Using scanning tunneling microscopy/spectroscopy combined with ab initio calculations, the structure and electronic properties of the as-grown phosphorus structures are followed. The progressive formation of a phosphorus electronic band in the conduction band region is followed. More strikingly, a partial flatband that appears only on the HexP phase characterized by a sharp peak in the electronic spectrum is observed. These bands arise from the hybridization of phosphorus and gold atoms. This novel phosphorus-based structure exhibits remarkable electronic properties due to gold mediated phosphorus-phosphorus electronic coupling. This work paves the way for new interface material developments with attractive electronicproperties.