Atomic-resolution Scanning Tunneling Microscopy Research Articles

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.

Cryogen-free modular scanning tunneling microscope operating at 4-K in high magnetic field on a compact ultra-high vacuum platform.

One of the daunting challenges in modern low temperature scanning tunneling microscopy (STM) is the difficulty of combining atomic resolution with cryogen-free cooling. Further functionality needs, such as ultra-high vacuum (UHV), high magnetic field (HF), and compatibility with μm-sized samples, pose additional challenges to an already ambitious build. We present the design, construction, and performance of a cryogen-free, UHV, low temperature, and high magnetic field system for modular STM operation. An internal vibration isolator reduces vibrations in this system, allowing for atomic resolution STM imaging while maintaining a low base temperature of ∼4K and magnetic fields up to 9T. Samples and tips can be conditioned in situ utilizing a heating stage, an ion sputtering gun, an e-beam evaporator, a tip treater, and sample exfoliation. In situ sample and tip exchange and alignment are performed in a connected UHV room temperature stage with optical access. Multisite operation without breaking vacuum is enabled by a unique quick-connect STM head design. A novel low-profile vertical transfer mechanism permits transferring the STM between room temperature and the low temperature cryostat.

Wavefront distortion correction in scanning tunneling microscope image.

We report an algorithm to identify and correct distorted wavefronts in atomic resolution scanning tunneling microscope images. This algorithm can be used to correct nonlinear in-plane distortions without prior knowledge of the physical scanning parameters, the characteristics of the piezoelectric actuator, or individual atom positions. The 2D image is first defined as a sum of sinusoidal plane waves, where a nonlinear distortion renders a curve for an otherwise ideal linear wavefront. Using the Fourier transforms of local areas of the image, the algorithm generates a wavefront vector field. The identified wavefronts are subsequently linearized for each plane wave without changing lattice orders, giving rise to distortion corrections. Our algorithm is complementary to conventional post-processing algorithms that require prior detection of real space features, which can also be used to correct nonlinear distortions in 2D images acquired by other microscopy techniques.

Atom-resolved imaging with a silicon tip integrated into an on-chip scanning tunneling microscope.

Limited throughput is a shortcoming of the Scanning Tunneling Microscope (STM), particularly when used for atomically precise lithography. To address this issue, we have developed an on-chip STM based on Microelectromechanical-Systems (MEMS) technology. The device reported here has one degree of freedom, replacing the Z axis in a conventional STM. The small footprint of the on-chip STM provides a great opportunity to increase STM throughput by incorporating a number of on-chip STMs in an array to realize parallel STM. The tip methodology adopted for the on-chip STM presented here, which is a batch-fabricated Si tip, makes our design conducive to this goal. In this work, we investigate the capability of this on-chip STM with an integrated Si tip for STM imaging. We integrate the on-chip STM into a commercial ultrahigh-vacuum STM system and perform imaging with atomic resolution on par with conventional STMs but at higher scan speeds due to the higher sensitivity of the MEMS actuator relative to a piezotube. The results attest that it is possible to achieve a parallel and high-throughput STM platform, which is a fully batch-fabricated MEMS STM nanopositioner capable of performing atomic-resolution STM imaging.

Atomic construction and spectroscopic characterization of FeSe-derived thin films on SrTiO3 substrates

Controllably fabricating low-dimensional systems and unraveling their exotic states at the atomic scale is a pivotal step for the construction of quantum functional materials with emergent states. Here, by utilizing the elaborated molecular beam epitaxy growth, we obtain various FexSey phases beyond the single-layer FeSe/SrTiO3 films. A synthetic strategy of lowering substrate temperature with superfluous Se annealing is implemented to achieve various stoichiometric FeSe-derived phases, ranging from 1:1 to 5:8. The phase transitions and electronic structure of these FexSey phases are systematically characterized by atomic resolution scanning tunneling microscopy measurements. We observe the long-ranged antiferromagnetic order of the Fe4Se5 phase by spin-polarized signals with striped patterns, which is also verified by their magnetic response of phase shift between adjacent domains. The electronic doping effect in insulating Fe4Se5 and the kagome effect in metallic Fe5Se8 are also discussed, where the kagome lattice is a promising structure to manifest both spin frustration of d electrons in a quantum-spin-liquid phase and correlated topological states with flat-band physics. Our study provides promising opportunities for constructing artificial superstructures with tunable building blocks, which is helpful for understanding the emergent quantum states and their correlation with competing orders in the FeSe-based family.

Magnetic Field-Induced Spin Nematic Phase Up to Room Temperature in Epitaxial Antiferromagnetic FeTe Thin Films Grown by Molecular Beam Epitaxy.

Electronic nematicity, where strong correlations drive electrons to align in a way that lowers the crystal symmetry, is ubiquitous among unconventional superconductors. Understanding the interplay of such a nematic state with other electronic phases underpins the complex behavior of these materials and the potential for tuning their properties through external stimuli. Here, we report magnetic field-induced spin nematicity in a model system tetragonal FeTe, the parent compound of iron chalcogenide superconductors, which exhibits a bicollinear antiferromagnetic order. The studies were conducted on epitaxial FeTe thin films grown on SrTiO3(001) substrates by molecular beam epitaxy, where the bicollinear antiferromagnetic order was confirmed by in situ atomic resolution scanning tunneling microscopy imaging. A 2-fold anisotropy is observed in in-plane angle-dependent magnetoresistance measurements, indicative of magnetic field-induced nematicity. Such 2-fold anisotropy persists up to 300 K, well-above the bicollinear antiferromagnetic ordering temperature of 75 K, indicating a magnetic field-induced spin nematic phase up to room temperature in the antiferromagnet FeTe.

Adsorption and Thermal Decomposition of Triphenyl Bismuth on Silicon (001).

We investigate the adsorption and thermal decomposition of triphenyl bismuth (TPB) on the silicon (001) surface using atomic-resolution scanning tunneling microscopy, synchrotron-based X-ray photoelectron spectroscopy, and density functional theory calculations. Our results show that the adsorption of TPB at room temperature creates both bismuth-silicon and phenyl-silicon bonds. Annealing above room temperature leads to increased chemical interactions between the phenyl groups and the silicon surface, followed by phenyl detachment and bismuth subsurface migration. The thermal decomposition of the carbon fragments leads to the formation of silicon carbide at the surface. This chemical understanding of the process allows for controlled bismuth introduction into the near surface of silicon and opens pathways for ultra-shallow doping approaches.

Imaging Field-Driven Melting of a Molecular Solid at the Atomic Scale.

Solid-liquid phase transitions are basic physical processes, but atomically-resolved microscopy has yet to capture their full dynamics. We have developed a new technique for controlling the melting and freezing of self-assembled molecular structures on a graphene field-effect transistor (FET) that allows phase transition behavior to be imaged using atomically-resolved scanning tunneling microscopy. This is achieved by applying electric fields to F4 TCNQ-decorated FETs to induce reversible transitions between molecular solid and liquid phases at the FET surface. Nonequilibrium melting dynamics are visualized by rapidly heating the graphene substrate with electrical current and imaging the resulting evolution toward new 2D equilibrium states. An analytical model has been developed that explains observed mixed-state phases based on spectroscopic measurement of solid and liquid molecular energy levels. The observed non-equilibrium melting dynamics are consistent with Monte Carlo simulations. This article is protected by copyright. All rights reserved.

Bismuth trichloride as a molecular precursor for silicon doping

Dopant impurity species can be incorporated into the silicon (001) surface via the adsorption and dissociation of simple precursor molecules. Examples include phosphine (PH3), arsine (AsH3), and diborane (B2H6) for the incorporation of phosphorus, arsenic, and boron, respectively. Through exploitation of precursor surface chemistry, the spatial locations of these incorporated dopants can be controlled at the atomic scale via the patterning of a hydrogen lithographic resist layer using scanning tunneling microscopy (STM). There is strong interest in the spatial control of bismuth atoms incorporated into silicon for quantum technological applications; however, there is currently no known precursor for the incorporation of bismuth that is compatible with this STM-based lithographic method. Here, we explore the precursor chemistry (adsorption, diffusion, and dissociation) of bismuth trichloride (BiCl3) on Si(001). We show atomic-resolution STM images of BiCl3 exposed Si(001) surfaces at low coverage and combine this with density functional theory calculations to produce a model of the surface processes and the observed features. Our results show that, at room temperature, BiCl3 completely dissociates to produce bismuth ad-atoms, ad-dimers, and surface-bound chlorine, and we explain how BiCl3 is a strong candidate for a bismuth precursor compound compatible with lithographic patterning at the sub-nanometer scale.

Atomic-Resolution Imaging of Micron-Sized Samples Realized by High Magnetic Field Scanning Tunneling Microscopy

Scanning tunneling microscopy (STM) can image material surfaces with atomic resolution, making it a useful tool in the areas of physics and materials. Many materials are synthesized at micron size, especially few-layer materials. Limited by their complex structure, very few STMs are capable of directly positioning and imaging a micron-sized sample with atomic resolution. Traditional STMs are designed to study the material behavior induced by temperature variation, while the physical properties induced by magnetic fields are rarely studied. In this paper, we present the design and construction of an atomic-resolution STM that can operate in a 9 T high magnetic field. More importantly, the homebuilt STM is capable of imaging micron-sized samples. The performance of the STM is demonstrated by high-quality atomic images obtained on a graphite surface, with low drift rates in the X-Y plane and Z direction. The atomic-resolution image obtained on a 32-μm graphite flake illustrates the new STM's ability of positioning and imaging micron-sized samples. Finally, we present atomic resolution images at a magnetic field range from 0 T to 9 T. The above advantages make our STM a promising tool for investigating the quantum hall effect of micron-sized layered materials.

Atomically resolved low-temperature scanning tunneling microscope operating in a 22 T water-cooled magnet

We present the design and construction of a nonmetallic tip-sample mechanical loop featured Scanning Tunneling Microscope (STM) that operates in a 22 T water-cooled magnet at a low temperature of l.8 K. The STM head mainly consists of a spider-drive motor, stand-alone scanner, moveable sapphire sample holder, and sapphire frame. All parts exist in the tip-sample mechanical loop are made of sapphire to reduce the interference from high magnetic fields. Except for the necessary movement of the tip and scanner, all STM parts are stationary. More importantly, the tip-sample mechanical loop is separate from the motor after detecting the tunneling current, which helps prevent the high voltage signal interference from entering the tip-sample junction, leading to a high stable imaging. A Janis liquid helium cryostat is used to obtain a variable temperature range from 1.8 K to 300 K, and the STM head is cooled down via helium exchange gas. The STM head hangs at the bottom of a probe with a two-stage spring suspension to prevent the huge vibration generated by the water-cooled magnet from entering the tip-sample junction. The performance is demonstrated by atomically resolved STM images of graphite surface at 0 T and 22.8 T under room temperature. Furthermore, the obtained atomic-resolution images of NbSe2 at 1.8 K and 22 T, as well as high-resolution dI/dV spectrums at temperatures from 1.8 K to 8.5 K and magnetic fields from 0 T to 22 T are displayed. This is the first STM capable of atomic-resolution imaging and dI/dV measurement at 1.8 K in a 22 T water-cooled magnet. The high immunity to the magnetic field makes the nonmetallic tip-sample mechanical loop widely useable for atomic-resolution STM imaging in ultra-high magnetic field conditions.

Development of a near-5-Kelvin, cryogen-free, pulse-tube refrigerator-based scanning probe microscope.

We report the design and performance of a cryogen-free, pulse-tube refrigerator (PTR)-based scanning probe microscopy (SPM) system capable of operating at a base temperature of near 5 K. We achieve this by combining a home-made interface design between the PTR cold head and the SPM head, with an automatic gas-handling system. The interface design isolates the PTR vibrations by a combination of polytetrafluoroethylene and stainless-steel bellows and by placing the SPM head on a passive vibration isolation table via two cold stages that are connected to thermal radiation shields using copper heat links. The gas-handling system regulates the helium heat-exchange gas pressures, facilitating both the cooldown to and maintenance of the base temperature. We discuss the effects of each component using measured vibration, current-noise, temperature, and pressure data. We demonstrate that our SPM system performance is comparable to known liquid-helium-based systems with the measurements of the superconducting gap spectrum of Pb, atomic-resolution scanning tunneling microscopy image and quasiparticle interference pattern of Au(111) surface, and non-contact atomic force microscopy image of NaCl(100) surface. Without the need for cryogen refills, the present SPM system enables uninterrupted low-temperature measurements.

Macro- and atomic-scale observations of a one-dimensional heterojunction in a nickel and palladium nanowire complex

The creation of low-dimensional heterostructures for intelligent devices is a challenging research topic; however, macro- and atomic-scale connections in one-dimensional (1D) electronic systems have not been achieved yet. Herein, we synthesize a heterostructure comprising a 1D Mott insulator [Ni(chxn)2Br]Br2 (1; chxn = 1R-2R-diaminocyclohexane) and a 1D Peierls or charge-density-wave insulator [Pd(chxn)2Br]Br2 (2) using stepwise electrochemical growth. It can be considered as the first example of electrochemical liquid-phase epitaxy applied to molecular-based heterostructures with a macroscopic scale. Moreover, atomic-resolution scanning tunneling microscopy images reveal a modulation of the electronic state in the heterojunction region with a length of five metal atoms (~ 2.5 nm), that is a direct evidence for the atomic-scale connection of 1 and 2. This is the first time that the heterojunction in the 1D chains has been shown and examined experimentally at macro- and atomic-scale. This study thus serves as proof of concept for heterojunctions in 1D electronic systems.

Electronic Properties and Carrier Dynamics at the Alloy Interfaces of WS2x Se2-2x Spiral Nanosheets.

Electronic properties at the interfaces between different-composition domains of 2D-alloys are key for their optical, electronic, and optoelectronic applications. Understanding the interfacial electronic structures and carrier dynamics is essential for designing and fabricating devices that use these alloys. Here, WS2x Se2-2x spiral nanosheets are prepared using the physical vapor deposition method, and the nonlinear optical and electronic properties, as well as the carrier dynamics at the interfaces between the WS and WSe domains, are studied. Second-harmonic generation tests demonstrate that these nanosheets exhibit a very strong layer-dependent nonlinear optical effect. Atomic-resolution scanning tunneling microscopy (STM) and spectroscopy (STS) measurements reveal that S and Se atoms are non-uniformly distributed, forming WS domains, WSe domains, and defect-related areas. Atomic STM images and STS maps reveal enhanced local density of states by electron scattering at the WS/WSe interfaces, providing a detailed nanoscale interpretation of the S/Se-ratio-dependent lifetimes observed in pump-probe spectroscopy measurements. This work provides valuable interfacial characterization of 2D-alloy materials, using state-of-the-art methods with high temporal and spatial resolutions. The obtained insights are likely to be useful for prospective applications.

Hexagonal approximant of the dodecagonal oxide quasicrystal on Pt(111)

Quasicrystals (QC) in condensed matter are often accompanied by competing periodic structures with large unit cells that approximate the QC. Likewise for the dodecagonal Ba-Ti-O oxide quasicrystal that forms on Pt(111), approximants with square and oblique lattices have been reported. Here we report on the identification of a hexagonal approximant for this QC. Atomically-resolved scanning tunneling microscopy shows the characteristic vertex atoms, which form triangle, square, and rhombus tiling elements, which organize into more complex motifs that are building blocks of the aperiodic QC. Low-energy electron diffraction confirms the large-cell hexagonal structure and is well reproduced by a minimal single-scattering calculation. To accommodate the misfit, the hexagonal layer is twisted $4{\phantom{\rule{0.16em}{0ex}}}^{\ensuremath{\circ}}$ against the hexagonal Pt(111) substrate, which also lowers the overall symmetry of the system.

Phase transition-induced superstructures of β-Sn films with atomic-scale thickness* *Project supported by the National Natural Science Foundation of China (Grant Nos. 61674045, 61911540074, and 21622304), the Fund from the Ministry of Science and Technology of China (Grant No. 2016YFA0200700), the Strategic Priority Research Program and Key Research Program of Frontier Sciences (Chinese Academy of Sciences) (Grant Nos. XDB30000000 and QYZDB-SSW-SYS031).

The ultrathin β-Sn(001) films have attracted tremendous attention owing to its topological superconductivity (TSC), which hosts Majorana bound state (MBSs) for quantum computation. Recently, β-Sn(001) thin films have been successfully fabricated via phase transition engineering. However, the understanding of structural phase transition of β-Sn(001) thin films is still elusive. Here, we report the direct growth of ultrathin β-Sn(001) films epitaxially on the highly oriented pyrolytic graphite (HOPG) substrate and the characterization of intricate structural-transition-induced superstructures. The morphology was obtained by using atomic force microscopy (AFM) and low-temperature scanning tunneling microscopy (STM), indicating a structure-related bilayer-by-bilayer growth mode. The ultrathin β-Sn film was made of multiple domains with various superstructures. Both high-symmetric and distorted superstructures were observed in the atomic-resolution STM images of these domains. The formation mechanism of these superstructures was further discussed based on the structural phase transition of β to α-Sn at the atomic-scale thickness. Our work not only brings a deep understanding of the structural phase transition of Sn film at the two-dimensional limit, but also paves a way to investigate their structure-sensitive topological properties.

Synthesis, Magnetic Properties, and Electronic Structure of Magnetic Topological Insulator MnBi2Se4.

The intrinsic magnetic topological insulators MnBi2Te4 and MnBi2Se4 support novel topological states related to symmetry breaking by magnetic order. Unlike MnBi2Te4, the study of MnBi2Se4 has been inhibited by the lack of bulk crystals, as the van der Waals (vdW) crystal is not the thermodynamic equilibrium phase. Here, we report the layer-by-layer synthesis of vdW MnBi2Se4 crystals using nonequilibrium molecular beam epitaxy. Atomic-resolution scanning transmission electron microscopy and scanning tunneling microscopy identify a well-ordered vdW crystal with septuple-layer base units. The magnetic properties agree with the predicted layered antiferromagnetic ordering but disagree with its predicted out-of-plane orientation. Instead, our samples exhibit an easy-plane anisotropy, which is explained by including dipole-dipole interactions. Angle-resolved photoemission spectroscopy reveals the gapless Dirac-like surface state, which demonstrates that MnBi2Se4 is a topological insulator above the magnetic-ordering temperature. These studies show that MnBi2Se4 is a promising candidate for exploring rich topological phases of layered antiferromagnetic topological insulators.

Antimony allotropes fabricated on oxide layer of Cu(111)

Monolayer and few layer antimony allotropes fabricated on oxide layers are essential for practical applications in fields of solar cells, electronic and photonic devices. Here the antimony structural phases are systemically studied on corrugated copper oxide of Cu(111) by atomically-resolved scanning tunneling microscopy (STM). We find that initial deposition of Sb atoms causes the structural changes of the underlying oxide layer and sequentially gives rise to the formation of flat (√7 × √7)-Sb and buckled antimonene phases. Finally, a nanoring-like antimony configuration is observed with triangle-shaped atomic arrays closely packing and shows high stabilities for oxygen exposure. The (√7 × √7) phase exhibits the metallic property with energetically continuous electronic states existing near Fermi level. For the antimonene and nanoring phases, band gap signatures are observed, implying the semiconducting features. Our results provide a method for fabricating stable elemental allotropes on oxide surfaces.

Atomic structures and electronic properties of Cr-doped ZnO() surfaces

An integrated approach combining scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS) is used to investigate the atomic structures and electronic properties of Cr-doped ZnO(▪) surfaces. When deposited at 300 K, Cr at low surface coverage (< 0.1 ML) appeared either as isolated atoms on the surface terrace of ZnO(▪) or substituting Zn atoms in the ZnO lattice. Their structural models could be identified from atomic-resolution STM images and their oxidation states were found as Cr3+ based on XPS measurements. Rectangular islands nucleated at step edges along the [0001] direction could also be observed during the initial growth of Cr at 300 K and were assigned as Cr islands. The density of Cr islands as well as their average size increased with the increasing of Cr surface loading. Thermal treatments at above 600 K could facilitate the decomposition of Cr islands and the re-dispersion of Cr atoms into the ZnO lattice, indicating a strong interaction between Cr and ZnO. The adsorption of CO at 78 K showed no preferential adsorption at Cr3+ sites embedded in the surface lattice of ZnO. However, the re-dispersion of Cr atoms into the ZnO bulk at above 600 K could induce a significant upward band bending, causing a negative shift of core level XPS peaks of Zn 2p and O 1s by ~0.5–0.7 eV. Our study has thus constructed a model catalyst for Cr-doped ZnO and provided atomic insight for understanding ZnO-based catalysts.

Structure of one-dimensional monolayer Si nanoribbons on Ag(111)

One-dimensional silicon nanoribbons (SiNRs) have the potential for application to future electronic devices because of their compatibility with current silicon-based electronic devices and their theoretical outstanding electronic properties, such as the size-dependent band gap. Here we grew SiNRs by the deposition of Si on a Ag(111) surface. We investigated SiNRs on the Ag(111) surface using a combination of scanning tunneling microscopy (STM), atomic force microscopy (AFM), and density functional theory (DFT) calculations. The atomic resolution STM and AFM images revealed that SiNRs have the same width and align along the equivalent orientations of Ag(111). The main body of SiNRs was found to be symmetric about the long axes of the ribbons, but the terminals of SiNRs break the symmetry. The DFT calculation results revealed a buckled single-layer structure of SiNRs, which is composed of Si hexagonal and tetragonal rings.