Scanning Tunneling Microscopy Results Research Articles

Interfacial Engineering of Mn Porphyrin/Au Electrodes for Identifying MnOx as the Active Species under Oxygen Evolution Reactions.

Understanding the influence of surface structural features at a molecular level is beneficial in guiding an electrode's mechanistic proposals for electrocatalytic reactions. The relationship between structural stability and catalytic activity significantly impacts reaction performance, even though atomistic knowledge of active sites remains a topic of discussion. In this context, this work presents scanning tunneling microscopy (STM) results for the highly ordered arrangement of manganese porphyrin molecules on a Au(111) surface; STM allows us to monitor active sites at a molecular level to focus on long-standing issues with the electrocatalytic process, especially the exact nature of the real active sites at the interfaces. After water oxidation, manganese porphyrin rapidly decomposes into active catalytic species as bright protrusions. These newly formed active species drastically lost catalytic activity, up to 82%, through only acid treatment, one of the oxide removal methods, not by deionized water and acetone treatments. STM results of the obviated active species on the Au surface by an acidic solution support the forfeited catalytic activity. In addition, it shows a 67% decrement in catalytic activity by adsorption of phosphonic acid, one of the oxide's preferred adsorption materials, compared to the pristine one. Based on these observations, we confirm that the newly formed active species, as water oxidation catalysts, mostly consist of manganese oxides. Notable findings of our work provide molecular evidence for the active sites of Au and modified Au electrodes that spur the future development of water oxidation catalysts.

Quasicrystalline Antimony Thin Films

AbstractThe growth of antimony (Sb) thin films on the fivefold surface of icosahedral Ag−In−Yb quasicrystal has been studied by scanning tunneling microscopy (STM) and x‐ray photoelectron spectroscopy (XPS). At low coverage, the deposited Sb yields a network of pentagons of different sizes and heights. These Sb pentagons can be mapped by a pentagonal tiling of the substrate and thus exhibit quasicrystalline long‐range order. Subsequent deposition of Sb yields a disordered film. XPS observations of the growth mode are consistent with the STM results.

Weak dimensionality dependence of charge density wave transition in 2H-NbSe2

The effect of dimensionality on charge density wave (CDW) transition temperature (TCDW) in 2H-NbSe2 is still under debate. Raman measurements uncovered highly enhanced TCDW for few-layer samples, while scanning tunneling microscopy results suggest comparable value of bulk crystals. Here, we obtained high-quality crystals of 2H-NbSe2 with residual resistivity ratio up to 120 and processed thin flakes by mechanical exfoliation. Electrical resistance measurements were carried out on crystals with different thickness to monitor the dimensionality dependence of TCDW, superconducting Tc, and upper critical field Hc2. It is revealed that when the bulk crystal evolves into few layers, the TCDW only increases slightly, though the variations of Tc and upper critical field Hc2 are consistent with previous results. The observed weak dependence of long-range CDW order on dimensionality agrees well with the recent theoretical calculations on anharmonic spectra. These results reconcile experiment and theory, and thus shed light on the mechanism of CDW for thin flakes of 2H-NbSe2.

Tunable bandgap of black phosphorus by arsenic substitution toward high-performance photodetector

Multilayer black phosphorus (BP) has been widely used in many infrared applications due to its narrow bandgap below 3.7-µm wavelength range. Approaches that reduce the bandgap to less than 0.33 eV would extend the cutoff wavelength and are of paramount importance. Moreover, the poor air stability of BP severely limits its practical applications. However, none of the current methods ensure effective bandgap tuning while enhancing air stability of BP for long-term device operation. This paper solved both problems by substituting BP with congener arsenic (As) atoms. We achieved millimeter-sized As-substituted BP (b-AsxP1−x) by optimizing the chemical vapor transport parameters, with As concentrations (x) varying as 0, 0.3, 0.4, 0.5, and 0.6. According to the scanning tunneling microscopy results, arsenic atoms are resolved to be randomly embedded in the phosphorus host lattice, while maintaining a well-ordered lattice arrangement. Therefore, the electrical bandgap of pristine BP is narrowed to ∼0.16 ± 0.02 eV for the b-As0.6P0.4 sample, accompanied by the accumulated p-doping and red-shifting BP Raman feature. Furthermore, the device based on b-As0.6P0.4 exhibits no signs of oxidation under ambient conditions (temperature ∼20°C; humidity ∼33%) for 48 h and shows a photoresponsivity of up to ∼882 mA W−1, exceeding the values of ∼314 mA W−1 for pristine BP devices due to the strong doping without obvious lattice distortion. Our findings indicate that arsenic-substituted BP has potential application in developing ambient-stable photodetectors and optical modulators.

Formation and Thermal Stability of Ordered Self-Assembled Monolayers by the Adsorption of Amide-Containing Alkanethiols on Au(111).

We examined the surface structure, binding conditions, electrochemical behavior, and thermal stability of self-assembled monolayers (SAMs) on Au(111) formed by N-(2-mercaptoethyl)heptanamide (MEHA) containing an amide group in an inner alkyl chain using scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and cyclic voltammetry (CV) to understand the effects of an internal amide group as a function of deposition time. The STM study clearly showed that the structural transitions of MEHA SAMs on Au(111) occurred from the liquid phase to the formation of a closely packed and well-ordered β-phase via a loosely packed α-phase as an intermediate phase, depending on the deposition time. XPS measurements showed that the relative peak intensities of chemisorbed sulfur against Au 4f for MEHA SAMs formed after deposition for 1 min, 10 min, and 1 h were calculated to be 0.0022, 0.0068, and 0.0070, respectively. Based on the STM and XPS results, it is expected that the formation of a well-ordered β-phase is due to an increased adsorption of chemisorbed sulfur and the structural rearrangement of molecular backbones to maximize lateral interactions resulting from a longer deposition period of 1 h. CV measurements showed a significant difference in the electrochemical behavior of MEHA and decanethiol (DT) SAMs as a result of the presence of an internal amide group in the MEHA SAMs. Herein, we report the first high-resolution STM image of well-ordered MEHA SAMs on Au(111) with a (3 × 2√3) superlattice (β-phase). We also found that amide-containing MEHA SAMs were thermally much more stable than DT SAMs due to the formation of internal hydrogen networks in MEHA SAMs. Our molecular-scale STM results provide new insight into the growth process, surface structure, and thermal stability of amide-containing alkanethiols on Au(111).

Embedded pseudo graphene nanoribbons oriented via Ge(110) surface reconstruction

Graphene nanoribbon, which is the one-dimensional form of graphene, is an attractive nano structure for next generation electronic devices. Herein, we studied the electronic properties of pseudo-GNRs in large-scale graphene sheets grown on Ge(110) using low temperature scanning tunneling microscopy (STM) and spectroscopy (STS). Based on our STM results, the pseudo-GNRs are aligned in the <112> direction of the Ge surface; the alignment of the pseudo-GNRs is controlled by the surface reconstruction of Ge(110) substrate, which can be an important merit in terms of the mass fabrication. Bandgap energies ranging from ∼0.12 to ∼0.3 eV were measured via STS on pseudo-GNRs in graphene/Ge(110), while the surrounding graphene area outside the pseudo-GNR growth region shows the typical electronic structure of graphene, verifying the spontaneous formation of metallic-semiconducting-metallic junction nanostructure. This study unveils the geometric and electronic properties of pseudo-GNRs in graphene/Ge(110), providing essential information for the realization of next-generation nanoelectronic devices. • Pseudo-GNRs aligned in the <112> direction on Ge surface. • Alignment controlled by surface reconstruction of Ge substrate. • Bandgap energies from ∼0.12 to ∼0.3 eV measured via STS on pseudo-GNRS. • Graphene outside growth regions showed typical electronic structure of graphene.

Scanning tunneling microscopy of Bi2Te3 films prepared by pulsed laser deposition: from nanocrystalline structures to van der Waals epitaxy

Bi2Te3 is a material with high efficiency of thermoelectric energy conversion. Recently, it was also recognized as a topological insulator, and is often used as the basis for creation of other types of topological matter. Pulsed laser deposition (PLD) is widely considered as a simple method for growing of multicomponent films, but not as a tool for van der Waals epitaxy. We demonstrate here that the van der Waals epitaxy of Bi2Te3 is indeed impossible in vacuum PLD, but is possible in the presence of a background gas, which is confirmed by the results of scanning tunneling microscopy and spectroscopy studies. Results of ab initio calculations reproduce tunneling spectra of the first three terraces of epitaxial films of Bi2Te3. In addition, an unusual hexagonal superstructure resembling a charge-density wave is observed in overheated films.

Magnetism engineering of nanographene: An enrichment strategy by co-depositing diverse precursors on Au(111)

The magnetism of nanographene is dominated by the structure of its carbon skeleton. However, the magnetism engineering of nanographene is hindered due to finite precursors. Here, we demonstrate an ingenious synthetic strategy to engineer the magnetism of nanographene through hetero-coupling two precursors on Au(111) surface. Bond-resolved scanning tunneling microscopy and spectroscopy results show that two homo-coupled products host a closed-shell structure, while the products with five membered ring defects perform as an open-shell one with the total spin number of 1/2, confirmed by spin-polarized density functional theory calculations. While two hetero precursors on Au(111) substrate, the hetero-coupled products both perform as the magnetic structure with total spin quantum numbers of 1/2 and 1, resulting from carbon skeleton transformations. Our work provides an effective way to engineer the magnetism of nanographene by enriching the magnetic products simultaneous, which could be extended into other controllable magnetic nanographene instruction.

C 3-symmetric truxene discotic liquid crystals with mixed ether chains: synthesis, mesomorphism, and self-assembly properties

ABSTRACT Nine new C3-symmetric 2,7,12-tris(decanoxy)-3,8,13-tris(alkoxy)truxene discogens were synthesized, and all exhibited only one three-dimensionally ordered hexagonal columnar mesophase with a wide mesogenic temperature range, as characterized by polarizing optical microscopy, differential scanning calorimetry, and X-ray diffractometry. Crucially, as the length of the alkoxy chain increased, the melting points first increased and then decreased, and, at the same time, the temperatures of the clearing point decreased gradually. In addition, these compounds were found to be highly thermally stable, having decomposition temperatures occurring well above 350°C, as determined by thermogravimetric analysis. The self-assembly behaviors in solution were studied using variable-concentration 1H-NMR, revealing that the truxenes self-aggregated in solution via the π–π facial interactions of the polycyclic aromatic units, and scanning tunneling microscopy results revealed that one of the discotic liquid crystal compounds periodically assembled in a hexagonal geometry at the liquid–solid interface of highly oriented pyrolytic graphite.

Understanding the Surface Structure and Catalytic Activity of SnOx/Au(111) Inverse Catalysts for CO2 and H2 Activation

Carbon dioxide hydrogenation is a promising approach for the reduction of greenhouse gas pollution via the production of fuels and high-value chemicals utilizing C1 chemistry. In this process, the activation of nonpolar molecules, CO2 and H2, at mild conditions is challenging. Herein, we report a well-defined inverse SnOx/Au(111) catalyst that shows the ability to activate both CO2 and H2 at room temperature. Scanning tunneling microscopy (STM) and ambient pressure X-ray photoemission spectroscopy (AP-XPS) are combined to understand the surface structure, growth mode, chemical state, and activity of SnOx/Au(111) surfaces. Nanostructures of SnOx at the sub-monolayer level were prepared by depositing Sn on Au(111) followed by O2 oxidation. For the as-prepared SnOx/Au(111), two-dimensionally formed SnOx thin films on a Au(111) substrate were observed with STM of two different moieties, discernible based on their height: clusters (∼0.4 Å) and nanoparticles (NPs, 1–2.5 Å), which are assigned to Sn–Au alloys and SnOx, respectively, in corroboration with XPS analysis. Furthermore, SnOx/Au(111) was annealed under UHV to test its thermal stability. Upon annealing at 400–600 K, a disappearance of SnOx NPs and reappearance of highly dispersed Sn clusters were clearly noticeable from the STM and XPS results, identifying the thermal decomposition of SnOx and subsequent formation of Sn–Au alloys on the surface due to the recombination of Sn clusters with Au. We investigated the reactivity of the SnOx/Au(111) surfaces toward CH4, CO2, and H2. The SnOx/Au(111) surfaces have excellent CO2 and H2 activation abilities even at room temperature with negligible reactivity for methane activation. Our AP-XPS results show that H2 can be activated on the SnOx NPs by the reduction to Sn. For CO2, the activation and further dissociation are identified by a reoxidation of Sn with newly formed Sn–O bonds and the formation of surface carbon. Therefore, we propose that SnOx is a potential catalyst or additive to achieve CO2 hydrogenation under mild conditions.

Sublattice Dependence and Gate Tunability of Midgap and Resonant States Induced by Native Dopants in Bernal-Stacked Bilayer Graphene.

The properties of semiconductors can be crucially impacted by midgap states induced by dopants, which can be native or intentionally incorporated in the crystal lattice. For Bernal-stacked bilayer graphene (BLG), which has a tunable band gap, the existence of midgap states induced by dopants or adatoms has been investigated theoretically and observed indirectly in electron transport experiments. Here, we characterize BLG midgap states in real space, with atomic-scale resolution with scanning tunneling microscopy and spectroscopy. We show that the midgap states in BLG-for which we demonstrate gate tunability-appear when the dopant is hosted on the nondimer sublattice sites. We further evidence the presence of narrow resonances at the onset of the high-energy bands (valence or conduction, depending on the dopant type) when the dopants lie on the dimer sublattice sites. Our results are supported by tight-binding calculations that agree remarkably well with the experimental findings.

Self‐Assembled Monolayers of Alkanethioacetates on Au(111) in Ammonium Hydroxide Solution

To shed light on the effects of NH4OH deprotection reagent on the formation of self‐assembled monolayers (SAMs) from alkanethioacetates on Au(111), we examined the surface structure and adsorption conditions of SAMs on Au(111) prepared in a 1 mM octanethioacetate (C8SAc) methanol solution and in a 1 mM methanol solution formed after in situ deprotection of C8SAc by NH4OH. Scanning tunneling microscopy (STM) imaging revealed that direct adsorption of C8SAc on Au(111) created only disordered SAMs regardless of the polarity of solvent (methanol, DMF, and hexane). In contrast, highly ordered SAMs with a well‐ordered c(4 × 2) phase were formed via in situ deprotection of C8SAc by NH4OH (deprotection condition: 30.7 mM NH4OH, 323 K, and 3 h). X‐ray photoelectron spectroscopy measurements also showed that the SAMs formed via in situ deprotection show uniform adsorption, whereas those prepared by direct adsorption show very complicated adsorption, which agrees well with STM results.

A picture of pseudogap phase related to charge fluxes

Recently, charge density fluctuations or charge fluxes attract strong interests in understanding the unconventional superconductivity. In this paper, a new emergent configuration in cuprates is identified by density functional theory simulations, called the charge pseudoplane, which exhibits the property of confining the dynamic charge fluxes for higher superconducting transition temperatures. It further redefines the fundamental collective excitation in cuprates as pQon with the momentum-dependent and ultrafast localization-delocalization duality. It is shown that both pseudogap and superconducting phases can be born from and intertwined through the charge flux confinement property of the charge pseudoplane region. Our experimental simulations based on the new picture provide good agreements with previous angle resolved photoemission spectroscopy and scanning tunneling microscopy results. Our work thus opens a new perspective into the origin of the pseudogap phase and other related phases in cuprates, and further provides a critical descriptor to search and design higher temperature superconductors.

Suppression of nano-hydride growth on Nb(100) due to nitrogen doping.

Niobium superconducting radio frequency (SRF) cavities enable the operation of modern superconducting accelerator facilities. These cavities do not approach the theoretical performance limits of Nb due to the deleterious effects of surface defects and chemical inhomogeneities such as Nb hydrides. Nitrogen doping is known to consistently increase the cavity performance and inhibit Nb hydride growth, but a comprehensive understanding of Nb hydride growth and suppression is not yet realized. Scanning tunneling microscopy (STM), scanning tunneling spectroscopy (STS), and density functional theory (DFT) calculations presented herein elucidate the real-time, nanoscale structural and electronic evolution of undoped, hydrogen doped, and hydrogen and nitrogen doped Nb(100) due to the growth and suppression of Nb nano-hydrides. DFT calculations in agreement with the experimental data found unique near-surface phases stabilized upon dopant incorporation. The experimental STM and STS results and DFT calculations reported herein provide the first in situ and real-time nanoscale visualization and characterization of the effects of nitrogen doping on Nb hydride suppression and growth. Such information allows for further optimization of nitrogen doping procedures and advances in the performance of SRF materials for next-generation SRF-based accelerators and free electron lasers.

ESPLORANDO “FLATLANDIA”: DAL GRAFENE ALLA SCOPERTA DI NUOVI MATERIALI BI-DIMENSIONALI

The development of nanotechnology has encouraged the research of new nanomaterials for innovative applications. In 2004, the production and study of graphene — that is a single layer of carbon atoms — showed, for the first time, the extraordinary properties of this material and opened the way to the exploration of the so-called two-dimensional (2D) materials. Since then, several 2D materials have been produced and studied, revealing properties and behaviours, in general, very different from those of corresponding bulk materials. Research on 2D materials is nowadays one of the most active and promising fields of materials science, which is setting the basis for the development of novel technologies, such as in electronics, optoelectronics, energy and molecular sensing. In this paper, some important aspects of the study of 2D materials will be introduced — such as the synthesis methodologies and characterization techniques — and some of their properties will be shown, with the support of recent experimental results of scanning tunneling microscopy (STM) investigations.

Contrast Reversal in Scanning Tunneling Microscopy and Its Implications for the Topological Classification of SmB6.

SmB6 has recently attracted considerable interest as a candidate for the first strongly correlated topological insulator. Such materials promise entirely new properties such as correlation-enhanced bulk bandgaps or a Fermi surface from spin excitations. Whether SmB6 and its surface states are topological or trivial is still heavily disputed however, and a solution is hindered by major disagreement between angle-resolved photoemission (ARPES) and scanning tunneling microscopy (STM) results. Here, a combined ARPES and STM experiment is conducted. It is discovered that the STM contrast strongly depends on the bias voltage and reverses its sign beyond 1 V. It is shown that the understanding of this contrast reversal is the clue to resolving the discrepancy between ARPES and STM results. In particular, the scanning tunneling spectra reflect a low-energy electronic structure at the surface, which supports a trivial origin of the surface states and the surface metallicity of SmB6 .

Anisotropic surface phonon dispersion of a deuterium-terminated Si(110)-(1 × 1) surface studied by high-resolution electron-energy-loss spectroscopy and first-principles calculations: Isotope effect

The surface phonon dispersion of a deuterium-terminated Si(110)-(1 × 1) surface [D:Si(110)-(1 × 1)] is investigated by using high-resolution electron-energy-loss spectroscopy (HREELS) and first-principles calculations based on the density functional theory (DFT) with the local density approximation (LDA). The characteristics of D:Si(110)-(1 × 1) are unique compared to those of H:Si(110)-(1 × 1) (Matsushita et al., 2015) in terms of the resolved vibrational modes. By the HREELS, one-dimensional surface phonons consisting of D–Si stretching vibrations are observed above the bulk-phonon band energy edge of 64.5 meV. Ten modes are observed below this value, classified as surface, surface resonant, and bulk phonons according to the calculated energy dispersion as well as the depth profile of spectral density and displacement vectors. In particular, five D–Si bending modes are observed out of the seven theoretically predicted modes. The bending modes are strongly coupled with the displacements across the D and five Si layers. The DFT-LDA surface phonon dispersion is in good agreement with the experimental results except a few frequency/dispersion mismatches, as the structure optimized by DFT-LDA mismatches with the previous scanning tunneling microscopy (STM) results (Matsushita et al., 2015). D:Si(110)-(1 × 1) elucidates the nature of covalently bonded phonons and their characteristics both experimentally and theoretically.

Advances in E-ALD By Slrr for the Growth of Ultra Thin Films of Metal and Alloys - in Recognition to John Stickney's Contribution to Electrodeposition

The idea realization progress of electrochemical atomic layer deposition by surface limited redox replacement (E-ALD by SLRR) is among the brightest and most significant contributions of Professor John Stickney. The approach proposed by him in early nineties of last century for epitaxial growth of compound semiconductor films was extended in the beginning of 21st century with his active participation and contribution to the deposition of ultra thin coatings of metals and alloys with a variety of applications thus establishing foundation for the development of one of the most useful and versatile thin film growth methods. In the beginning of this presentation an overview of existing approaches for epitaxial metal thin film growth along with E-ALD by SLRR will first be presented. A comparison of the kinetics manipulation approaches will be made with emphasis on the ability of those methods to produce epitaxial, flat and uniform deposits. In the course of this comparison illustrations will be provided with results, illustrating the advantages and limitations of these deposition approaches in the growth of Ag and Cu thin films on Au (111) substrates. To support the discussion, on the approaches employed, results of electrochemical, in-situ scanning tunneling microscopy (STM), X-ray Photoelectron Spectroscopy characterization experiments will be presented and compared. In the second part, the applicability of SLRR and electroless SLRR in the growth of Pt and Pd on Au (111) substrate will be discussed with special emphasis on the contribution and achievements of John Stickney’s research team. Experimentally demonstrated will be the SLRR growth of Pt and Pd layers with controllable thickness taking place in “shuttling” chamber, flow cell, and “one-pot” configuration. Open circuit potentiometry during the replacement reaction will be shown as a way to control the completion of each deposition event. Anodic stripping of the entire multilayer will be used for determining the overall film thickness. Cyclic Voltammetry and STM will be employed to characterize the growth of Pt and Pd layers with up to 10 nm thickness. High-resolution STM results and modelling concepts underlying the foundation of the proposed approaches will shed light on the mechanistic aspects associated with the nature of growth by redox exchange at a monolayer level. In the third component of this presentation an overview of recent work on the design of potent catalysts with application in energy production and storage will be presented. This will include the use of SLRR approach for coating nanoparticles and continuous nanoporous metal layers with ultra thin films of metal / alloy with specific functionality. Successful outcome of this coating renders the final product catalytically active. In this part, a brief description will be provided also on the direct use of SLRR based protocols for the smart design of bimetallic alloy and/or core shell clusters with application in the most commonly used reactions in the field of fuel-cell catalysis. The discussion on the synthetic component of all relevant activities will be concluded with demonstration of results of testing of accordingly developed catalysts. Finally, a glimpse into the future of this rapidly developing field will be also provided.

Method combining scanning tunneling microscopy and atom probe tomography for observing inside of materials

In this paper, we demonstrate the feasibility of a method combining scanning tunneling microscopy (STM) and atom probe tomography (APT). In this method, an atomically smooth or flat surface for STM observation is prepared by field evaporation using an APT system. The chemical composition of the surface obtained by APT can be used to analyze the results of STM. By developing this method, it is expected that local and very fine structures inside materials can be observed with true atomic resolution. We also demonstrate that nanoscale corrugation, which has a strong effect on the reconstruction procedure in the analysis of APT data, can be observed by STM.

Amorphous Carbon-Induced Surface Defect Repair for Reinforcing the Mechanical Properties of Carbon Fiber.

Graphene oxide (GO) was prepared using metal-catalyzed crystallization of amorphous carbon on a carbon fiber surface to improve the mechanical properties of the carbon fiber (CF). The deposited GO was used for repairing of surface structure defects on CF, thereby improving the tensile strength and interfacial strength force of CF. The grown morphology of GO and the changes in CF surface microstructure before and after remediation were investigated in detail by scanning tunneling microscopy and Raman spectroscopy. The effects of surface repair on the mechanical properties of the CF and the resulting composites were investigated systematically. The results of scanning tunneling microscopy show that the graphene oxide formed on the surface of carbon fiber present uniform dispersion. Raman spectroscopy curves indicate that CF successfully remediated the defects in the CF surface. The results of mechanical properties testing show that such a remediation method could significantly enhance the tensile strength of CF and increase the interfacial strength versus raw fibers; that is, the tensile strength of CF was enhanced by 42% and the interfacial strength by 33.7%.