Ultrahigh Vacuum Scanning Tunneling Research Articles

Influence of hydrogen-bonded 3-mercaptopropionic acid bilayers on binary self-assembled monolayer formation

The influence of the monolayer order, defect density, and bilayer formation on the formation of binary self-assembled monolayers (SAMs) was investigated via the solution-phase displacement of 3-mercaptopropionic acid (MPA) by 1-decanethiol (DT). The ultrahigh vacuum scanning tunneling microscopy results confirm that well-ordered, pristine MPA SAMs are displaced at slower rates than MPA SAMs with less long-range order and greater defect density. Furthermore, MPA samples containing regions of an MPA bilayer displayed the slowest rates of displacement with DT. For pristine MPA samples and MPA samples with regions of an MPA bilayer, displacement with DT resulted in the formation of the low-density, lying down phase of DT. Our results suggest that the presence of an MPA bilayer, the result of hydrogen bonding between carboxylic acid groups in MPA, significantly lowers the rate of total displacement of MPA by DT compared to moderately defected MPA SAMs. These results highlight the importance of the structure, composition, and intermolecular forces, such as hydrogen bonding, when considering binary SAM formation via solution-phase displacement methods.

Mapping the Slow Stabilization of End States with Length along a Laterally Extended Graphene Nanoribbon.

With a lateral bisnaphtho-extended chemical structure, finite 7-13 carbon atom wide armchair graphene nanoribbons (7-13-aGNRs) were on-surface synthesized. For all lengths up to N = 7 monomer units, low-temperature ultrahigh vacuum scanning tunneling spectroscopy and spatial dI/dV maps were recorded at each captured tunneling resonance. The degeneracy of the two central electronic end states (ESs) occurs in a slowly decaying regime with N converging toward zero for N = 6 long 7-13-aGNR (12 bonded anthracenes), while it is N = 2 (4 bonded anthracenes) for seven carbon atoms wide armchair GNRs (7-aGNRs). The two end dI/dV conductance maxima of ESs are also shifted away from strictly two ends of the 7-13-aGNR compared to the 7-aGNR. Using the quantum topology graph filiation between finite length polyacetylene and 7-13-aGNRs wires, we show that this slow decay of 7-13-aGNR ESs is coming from the property of the topological Hückel band matrix that expels the ESs into its eigenvalue spectrum gaps to keep harmony in the core spectrum.

Nanoscale Chemical Probing of Metal-Supported Ultrathin Ferrous Oxide via Tip-Enhanced Raman Spectroscopy and Scanning Tunneling Microscopy.

Metal-supported ultrathin ferrous oxide (FeO) has attracted immense interest in academia and industry due to its widespread applications in heterogeneous catalysis. However, chemical insight into the local structural characteristics of FeO, despite its critical importance in elucidating structure-property relationships, remains elusive. In this work, we report the nanoscale chemical probing of gold (Au)-supported ultrathin FeO via ultrahigh-vacuum tip-enhanced Raman spectroscopy (UHV-TERS) and scanning tunneling microscopy (STM). For comparative analysis, single-crystal Au(111) and Au(100) substrates are used to tune the interfacial properties of FeO. Although STM images show distinctly different moiré superstructures on FeO nanoislands on Au(111) and Au(100), TERS demonstrates the same chemical nature of FeO by comparable vibrational features. In addition, combined TERS and STM measurements identify a unique wrinkled FeO structure on Au(100), which is correlated to the reassembly of the intrinsic Au(100) surface reconstruction due to FeO deposition. Beyond revealing the morphologies of ultrathin FeO on Au substrates, our study provides a thorough understanding of the local interfacial properties and interactions of FeO on Au, which could shed light on the rational design of metal-supported FeO catalysts. Furthermore, this work demonstrates the promising utility of combined TERS and STM in chemically probing the structural properties of metal-supported ultrathin oxides on the nanoscale.

On Decorating a Honeycomb AlN Monolayer with Hydrogen and Fluorine Atoms: Ab Initio and Experimental Aspects.

Mono- and few-layer hexagonal AlN (h-AlN) has emerged as an alternative "beyond graphene" and "beyond h-BN" 2D material, especially in the context of its verification in ultra-high vacuum Scanning Tunneling Microscopy and Molecular-beam Epitaxy (MBE) experiments. However, graphitic-like AlN has only been recently obtained using a scalable and semiconductor-technology-related synthesis techniques, such as metal-organic chemical vapor deposition (MOCVD), which involves a hydrogen-rich environment. Motivated by these recent experimental findings, in the present work, we carried out ab initio calculations to investigate the hydrogenation of h-AlN monolayers in a variety of functionalization configurations. We also investigated the fluorination of h-AlN monolayers in different decoration configurations. We find that a remarkable span of bandgap variation in h-AlN, from metallic properties to nar-row-bandgap semiconductor, and to wide-bandgap semiconductor can be achieved by its hy-drogenation and fluorination. Exciting application prospects may also arise from the findings that H and F decoration of h-AlN can render some such configurations magnetic. We complemented this modelling picture by disclosing a viable experimental strategy for the fluorination of h-AlN.

Enantiopure molecules form apparently racemic monolayers of chiral cyclic pentamers.

Ultra-high vacuum scanning tunneling microscopy (UHV-STM) was used to investigate two related molecules pulse-deposited onto Au(111) surfaces: indoline-2-carboxylic acid and proline (pyrrolidine-2-carboxylic acid). Indoline-2-carboxylic acid and proline form both dimers and C5-symmetric "pinwheel" pentamers. Enantiomerically pure S-(-)-indoline-2-carboxylic acid and S-proline were used, and the pentamer structures observed for both were chiral. However, the presence of apparently equal numbers of 'right-' and 'left-handed' pinwheels is contrary to the general understanding that the chirality of the molecule dictates supramolecular chirality. A variety of computational methods were used to elucidate pentamer geometry for S-proline. Straightforward geometry optimization proved difficult, as the size of the cluster and the number of possible intermolecular interactions produced an interaction potential with multiple local minima. Instead, the Amber force field was used to exhaustively search all of phase space for chemically reasonable pentamer structures, producing a limited number of candidate structures that were then optimized as gas-phase clusters using density functional theory (DFT). The binding energies of the two lowest-energy pentamers on the Au(111) surface were then calculated by plane-wave DFT using the VASP software, and STM images predicted. These calculations indicate that the right- and left-handed pentamers are instead two different polymorphs.

Sub-5 nm Contacts and Induced p-n Junction Formation in Individual Atomically Precise Graphene Nanoribbons.

This paper demonstrates the fabrication of nanometer-scale metal contacts on individual graphene nanoribbons (GNRs) and the use of these contacts to control the electronic character of the GNRs. We demonstrate the use of a low-voltage direct-write STM-based process to pattern sub-5 nm metallic hafnium diboride (HfB2) contacts directly on top of single GNRs in an ultrahigh-vacuum scanning tunneling microscope (UHV-STM), with all the fabrication performed on a technologically relevant semiconductor silicon substrate. Scanning tunneling spectroscopy (STS) data not only verify the expected metallic and semiconducting character of the contacts and GNR, respectively, but also show induced band bending and p-n junction formation in the GNR due to the metal-GNR work function difference. Contact engineering with different work function metals obviates the need to create GNRs with different characteristics by complex chemical doping. This is a demonstration of the successful fabrication of precise metal contacts and local p-n junction formation on single GNRs.

Back focal plane imaging for light emission from a tunneling junction in a low-temperature ultrahigh-vacuum scanning tunneling microscope.

We report the design and realization of the back focal plane (BFP) imaging for the light emission from a tunnel junction in a low-temperature ultrahigh-vacuum (UHV) scanning tunneling microscope (STM). To achieve the BFP imaging in a UHV environment, a compact "all-in-one" sample holder is designed and fabricated, which allows us to integrate the sample substrate with the photon collection units that include a hemisphere solid immersion lens and an aspherical collecting lens. Such a specially designed holder enables the characterization of light emission both within and beyond the critical angle and also facilitates the optical alignment inside a UHV chamber. To test the performance of the BFP imaging system, we first measure the photoluminescence from dye-doped polystyrene beads on a thin Ag film. A double-ring pattern is observed in the BFP image, arising from two kinds of emission channels: strong surface plasmon coupled emissions around the surface plasmon resonance angle and weak transmitted fluorescence maximized at the critical angle, respectively. Such an observation also helps to determine the emission angle for each image pixel in the BFP image and, more importantly, proves the feasibility of our BFP imaging system. Furthermore, as a proof-of-principle experiment, electrically driven plasmon emissions are used to demonstrate the capability of the constructed BFP imaging system for STM induced electroluminescence measurements. A single-ring pattern is obtained in the BFP image, which reveals the generation and detection of the leakage radiation from the surface plasmon propagating on the Ag surface. Further analyses of the BFP image provide valuable information on the emission angle of the leakage radiation, the orientation of the radiating dipole, and the plasmon wavevector. The UHV-BFP imaging technique demonstrated here opens new routes for future studies on the angular distributed emission and dipole orientation of individual quantum emitters in UHV.

Improving MgO/Fe insulator-metal interface structure through oxygen-precoating of Fe(0 0 1)

We grew atomically flat and electronically uniform MgO island terraces on a Fe(001) whisker substrate precoated by a p(1 × 1) oxygen monolayer film. This interface engineering process increased about 10 times the size of MgO islands compared to the size of MgO islands directly grown on Fe(001), showing that the interface oxygen monolayer plays an essential role in MgO growth. Importantly, each squared-shape atomically flat MgO island includes only a few atomic defects, which provides high-quality insulating layers. Further, the MgO islands have an electronic decoupling functionality from the metal substrate. Surface morphology and local electronic structures were studied using a home-built ultrahigh vacuum scanning tunneling microscopy (STM) at a temperature of 5 K.

Planar tunneling spectroscopy on van der Waals superconductors with AlOx junction grown by atomic layer deposition

We demonstrate a method for fabricating a high-quality AlOx-based planar tunnel junction using atomic layer deposition, integrated with the exfoliation and transfer techniques for van der Waals (vdW) materials. The tunneling spectroscopy results on exfoliated Bi2Sr2CaCu2O8+δ and 2H-NbSe2 vdW superconductors are highly consistent with that obtained by ultrahigh vacuum scanning tunneling spectroscopy on atomically clean surfaces. The planar tunneling devices enable high-precision spectroscopy over a wide range of temperatures and magnetic fields and reveal novel features and stark contrast between high-TC cuprates and conventional superconductors. This method represents a universally applicable technique for probing the electronic structure of various two-dimensional vdW materials.

Scanning probe lithography on Ge(111)-c(2×8) surface

The paper describes nanometer scale lithography on atomically clean Ge(111)-c(2×8) surface performed in the ultra-high vacuum scanning tunneling microscope operating at 300 K. Using a standard Pt80Ir20 probe tip and applying bias voltages between 0.5 and 3 V, the Ge surface could be reliably imaged with atomic resolution without any modification of the sample. However, surface modification in highly localized area under the probe tip was observed at the bias voltages from 4 to 5 V. Such modification could occur in the form of the deposition of the tip material onto the scanned area of the sample, extraction of the sample material or generation of defects in the sample crystalline structure. Possible physical mechanisms of the processes outlined above as well as the strategies to achieve reliable scanning probe nanolithography are discussed.

Small molecule binding to surface-supported single-site transition-metal reaction centres

Despite dominating industrial processes, heterogeneous catalysts remain challenging to characterize and control. This is largely attributable to the diversity of potentially active sites at the catalyst-reactant interface and the complex behaviour that can arise from interactions between active sites. Surface-supported, single-site molecular catalysts aim to bring together benefits of both heterogeneous and homogeneous catalysts, offering easy separability while exploiting molecular design of reactivity, though the presence of a surface is likely to influence reaction mechanisms. Here, we use metal-organic coordination to build reactive Fe-terpyridine sites on the Ag(111) surface and study their activity towards CO and C2H4 gaseous reactants using low-temperature ultrahigh-vacuum scanning tunnelling microscopy, scanning tunnelling spectroscopy, and atomic force microscopy supported by density-functional theory models. Using a site-by-site approach at low temperature to visualize the reaction pathway, we find that reactants bond to the Fe-tpy active sites via surface-bound intermediates, and investigate the role of the substrate in understanding and designing single-site catalysts on metallic supports.

VO Cluster-Stabilized H2O Adsorption on a TiO2 (110) Surface at Room Temperature.

We probe the adsorption of molecular H2O on a TiO2 (110)-(1 × 1) surface decorated with isolated VO clusters using ultrahigh-vacuum scanning tunneling microscopy (UHV-STM) and temperature-programmed desorption (TPD). Our STM images show that preadsorbed VO clusters on the TiO2 (110)-(1 × 1) surface induce the adsorption of H2O molecules at room temperature (RT). The adsorbed H2O molecules form strings of beads of H2O dimers bound to the 5-fold coordinated Ti atom (5c-Ti) rows and are anchored by VO. This RT adsorption is completely reversible and is unique to the VO-decorated TiO2 surface. TPD spectra reveal two new desorption states for VO stabilized H2O at 395 and 445 K, which is in sharp contrast to the desorption of water due to recombination of hydroxyl groups at 490 K from clean TiO2(110)-(1 × 1) surfaces. Density functional theory (DFT) calculations show that the binding energy of molecular H2O to the VO clusters on the TiO2 (110)-(1 × 1) surface is higher than binding to the bare surface by 0.42 eV, and the resulting H2O-VO-TiO2 (110) complex provides the anchor point for adsorption of the string of beads of H2O dimers.

Chemical and Morphological Changes of Graphite Electrodes at Low Cathodic Potentials and Its Relevance to Li-Ion Batteries

Lithium-ion (Li-ion) batteries have become ubiquitous to modern-day electronics and electric vehicles. A detailed understanding regarding the reversible and irreversible nature of Li-ion electrode processes is a prerequisite to rationally delineate the factors affecting device performance and clarify degradation mechanisms. This includes, for instance, the role of electrode cracking and solid solid-electrolyte-interphase (SEI) formation which can contribute toward irreversible capacity loss. In terms of experimental approaches, aside from the high surface area electrodes used in practical systems, one powerful approach is to incorporate the study of well-defined electrodes and surface science techniques.1 Herein, we employ highly oriented pyrolytic graphite (HOPG) as a well-defined model anode in Li-ion batteries and reveal the chemical and morphological changes at low cathodic potentials prior to the potentials of bulk SEI formation.2 To achieve this, we employ the use of X-ray photoelectron spectroscopy (XPS) and ultrahigh vacuum scanning tunneling microscopy (UHV-STM). We utilize a so-called UHV-EC setup to provide a snapshot-like analysis of the electrode surface without the involvement of electrode washing or exposure to air.Upon cathodic polarization at ca. 1.75V (Figure 1), STM imaging shows the onset and occurrence of graphite exfoliation which can originate from the intercalation of solvated Li+ ions. Meanwhile, XPS shows a minimal amount of residual electrolyte along with the observation of LiF indicating the decomposition of the Li salt (LiPF6). The future extensions of our methodology and additional details will be provided at the presentation. Figure 1. (a) Cathodic linear sweep voltammogram in 1.1 M LiPF6 EC/DMC. Following polarization at ca. 1.75 V (b) STM imaging, and (c) XPS F 1s and Li 1s spectra.

A high-speed variable-temperature ultrahigh vacuum scanning tunneling microscope with spiral scan capabilities.

We present the design and development of a variable-temperature high-speed scanning tunneling microscope (STM). The setup consists of a two-chamber ultra-high vacuum system, including a preparation and a main chamber. The preparation chamber is equipped with standard preparation tools for sample cleaning and film growth. The main chamber hosts the STM that is located within a continuous flow cryostat for counter-cooling during high-temperature measurements. The microscope body is compact, rigid, and highly symmetric to ensure vibrational stability and low thermal drift. We designed a hybrid scanner made of two independent tube piezos for slow and fast scanning, respectively. A commercial STM controller is used for slow scanning, while a high-speed Versa Module Eurocard bus system controls fast scanning. Here, we implement non-conventional spiral geometries for high-speed scanning, which consist of smooth sine and cosine signals created by an arbitrary waveform generator. The tip scans in a quasi-constant height mode, where the logarithm of the tunneling current signal can be regarded as roughly proportional to the surface topography. Scan control and data acquisition have been programmed in the experimental physics and industrial control system framework. With the spiral scans, we atomically resolved diffusion processes of oxygen atoms on the Ru(0001) surface and achieved a time resolution of 8.3 ms per frame at different temperatures. Variable-temperature measurements reveal an influence of the temperature on the oxygen diffusion rate.

Chemically imaging nanostructures formed by the covalent assembly of molecular building blocks on a surface with ultrahigh vacuum tip-enhanced Raman spectroscopy

Surface-bound reactions have become a viable method to develop nanoarchitectures through bottom-up assembly with near atomic precision. However, the bottom-up fabrication of nanostructures on surfaces requires careful consideration of the intrinsic properties of the precursors and substrate as well as the complex interplay of any interactions that arise in the heterogeneous two-dimensional (2D) system. Therefore, it becomes necessary to consider these systems with characterization methods sensitive to such properties with suitable spatial resolution. Here, low temperature ultrahigh vacuum scanning tunneling microscopy (STM) and tip-enhanced Raman spectroscopy (TERS) were used to investigate the formation of 2D covalent networks via coupling reactions of tetra(4-bromophenyl)porphyrin (Br4TPP) molecules on a Ag(100) substrate. Through the combination of STM topographic imaging and TERS vibrational fingerprints, the conformation of molecular precursors on the substrate was understood. Following the thermally activated coupling reaction, STM and TERS imaging confirm the covalent nature of the 2D networks and suggest that the apparent disorder arises from molecular flexibility.

The scanning tunneling microscopy and spectroscopy of GaSb1– x Bi x films of a few-nanometer thickness grown by molecular beam epitaxy

The ultrahigh vacuum scanning tunneling microscope (STM) was used to characterize the GaSb1– x Bi x films of a few nanometers thickness grown by the molecular beam epitaxy (MBE) on the GaSb buffer layer of 100 nm with the GaSb (100) substrates. The thickness of the GaSb1– x Bi x layers of the samples are 5 and 10 nm, respectively. For comparison, the GaSb buffer was also characterized and its STM image displays terraces whose surfaces are basically atomically flat and their roughness is generally less than 1 monolayer (ML). The surface of 5 nm GaSb1– x Bi x film reserves the same terraced morphology as the buffer layer. In contrast, the morphology of the 10 nm GaSb1– x Bi x film changes to the mound-like island structures with a height of a few MLs. The result implies the growth mode transition from the two-dimensional mode as displayed by the 5 nm film to the Stranski–Krastinov mode as displayed by the 10 nm film. The statistical analysis with the scanning tunneling spectroscopy (STS) measurements indicates that both the incorporation and the inhomogeneity of Bi atoms increase with the thickness of the GaSb1– x Bi x layer.

Atomic precision imaging with an on-chip scanning tunneling microscope integrated into a commercial ultrahigh vacuum STM system

In this article, we replace the Z axis of the piezotube of a conventional Ultrahigh-Vacuum (UHV) Scanning Tunneling Microscope (STM) with a one-degree-of-freedom Microelectromechanical-System (MEMS) nanopositioner. As a result, a hybrid system is realized in which motions in the XY plane are carried out by the piezotube, while the MEMS device performs the Z-axis positioning with a smaller footprint and higher sensitivity. With the proposed system and a feedback loop, STM imaging is conducted on an H-passivated Si (100)-2×1 sample in a UHV condition, demonstrating that this on-chip STM is conducive to atomic precision scanning tunneling microscopy.

A millikelvin scanning tunneling microscope in ultra-high vacuum with adiabatic demagnetization refrigeration.

We present the design and performance of an ultra-high vacuum scanning tunneling microscope (STM) that uses adiabatic demagnetization of electron magnetic moments for controlling its operating temperature ranging between 30 mK and 1K with an accuracy of up to 7 μK rms. At the same time, high magnetic fields of up to 8T can be applied perpendicular to the sample surface. The time available for STM experiments at 50 mK is longer than 20 h, at 100 mK about 40 h. The single-shot adiabatic demagnetization refrigerator can be regenerated automatically within 7 h while keeping the STM temperature below 5K. The whole setup is located in a vibrationally isolated, electromagnetically shielded laboratory with no mechanical pumping lines penetrating its isolation walls. The 1K pot of the adiabatic demagnetization refrigeration cryostat can be operated silently for more than 20 days in a single-shot mode using a custom-built high-capacity cryopump. A high degree of vibrational decoupling together with the use of a specially designed minimalistic STM head provides outstanding mechanical stability, demonstrated by the tunneling current noise, STM imaging, and scanning tunneling spectroscopy measurements, all performed on an atomically clean Al(100) surface.

On-surface formation of metal–organic coordination networks with C⋯Ag⋯C and C=O⋯Ag interactions assisted by precursor self-assembly

Surface-bound reactions are commonly employed to develop nanoarchitectures through bottom-up assembly. Precursor molecules are carefully designed, and surfaces are chosen with the intention to fabricate low-dimensional extended networks, which can include one-dimensional and two-dimensional structures. The inclusion of functional groups can offer the opportunity to utilize unique chemistry to further tune the bottom-up method or form novel nanostructures. Specifically, carbonyl groups open up new avenues for on-surface coordination chemistry. Here, the self-assembly and formation of an organometallic species via the thermally induced reaction of 3,6-dibromo-9,10-phenanthrenequinone (DBPQ) molecules were studied on Ag(100) and Ag(110). Low-temperature ultrahigh vacuum scanning tunneling microscopy revealed the room temperature formation of self-assemblies defined by hydrogen and halogen bonds on Ag(100). Following a thermal anneal to 300 °C, DBPQ on Ag(100) was found to form metal-organic coordination networks composed of a combination of organometallic species characteristics of Ullmann-like coupling reactions and carbonyl complexes. On Ag(110), the C-Br bonds were found to readily dissociate at room temperature, resulting in the formation of disordered organometallic species.

Nanoscale Probing of Image-Potential States and Electron Transfer Doping in Borophene Polymorphs.

Because synthetic 2D materials are generally stabilized by interfacial coupling to growth substrates, direct probing of interfacial phenomena is critical for understanding their nanoscale structure and properties. Using field-emission resonance spectroscopy with an ultrahigh vacuum scanning tunneling microscope, we reveal Stark-shifted image-potential states of the v1/6 and v1/5 borophene polymorphs on Ag(111) with long lifetimes, suggesting high borophene lattice and interface quality. These image-potential states allow the local work function and interfacial charge transfer of borophene to be probed at the nanoscale and test the widely employed self-doping model of borophene. Supported by apparent barrier height measurements and density functional theory calculations, electron transfer doping occurs for both borophene phases from the Ag(111) substrate. In contradiction with the self-doping model, a higher electron transfer doping level occurs for denser v1/6 borophene compared to v1/5 borophene, thus revealing the importance of substrate effects on borophene electron transfer.