Low-temperature Scanning Tunneling Microscopy Research Articles

Self-Intercalated 1T-FeSe2 as an Effective Kagome Lattice.

In kagome lattice, with the emergence of Dirac cones and flat band in electronic structure, it provides a versatile ground for exploring intriguing interplay among frustrated geometry, topology and correlation. However, such engaging interest is strongly limited by available kagome materials in nature. Here we report on a synthetic strategy of constructing kagome systems via self-intercalation of Fe atoms into the van der Waals gap of FeSe2 via molecular beam epitaxy. Using low-temperature scanning tunneling microscopy, we unveil a kagome-like morphology upon intercalating a 2 × 2 ordered Fe atoms, resulting in a stoichiometry of Fe5Se8. Both the bias-dependent STM imaging and theoretical modeling calculations suggest that the kagome pattern mainly originates from slight but important reconstruction of topmost Se atoms, incurred by the nonequivalent subsurface Fe sites due to the intercalation. Our study demonstrates an alternative approach of constructing artificial kagome structures, which envisions to be tuned for exploring correlated quantum states.

Iodine-Induced Self-Assembly Structure Transition of Organic Molecules on the Ag(111) Surface

Iodine adsorption on metal surfaces has been extensively studied, but iodine’s effect on modulating the self-assembly structures of organic molecules has been less discussed. Here, we used low-temperature scanning tunneling microscopy and density functional theory to systematically study the self-assembly structure transformation of organic molecules affected by iodine dosing on the Ag(111) surface. We chose 2,6-naphthalenedicarboxylic acid and persilylated hexaethynylbenzene molecules and their reaction products as models to explore the changes in the molecular self-assembly structures on the Ag(111) surface induced by iodine deposition. Some new self-assembly structures are obtained by depositing iodine onto the molecules’ co-covered surface at different stages. These findings show that iodine can modulate the self-assembly structure of organic molecules with a weak intermolecular interaction, while those with a stronger intermolecular hydrogen bonding are not affected. The trend is verified with the density functional theory calculations.

Dimensional crossover of charge order in IrTe2 with strong interlayer coupling

Tuning dimensionality in van der Waals materials with finite interlayer coupling has introduced various electronic phase transitions by conventional mechanical exfoliation. Particularly when the electronic order is tied to the modulation of the interlayer coupling, such dimensional tunability has a strong impact on its stability and properties, which has rarely been investigated experimentally. Here, we demonstrate a dimensional crossover of charge order in IrTe$_2$ from genuine two- to quasi-three-dimension using low-temperature scanning tunneling microscopy and spectroscopy. Employing atomically thin IrTe$_2$ flakes ranging from monolayer to multilayer, we observe a gradual phase transition of charge order and exponential decay of Coulomb gap with increasing thickness. Moreover, we find a suppression of the density of states emerging at an abrupt lateral interface between two- and three-dimension. These findings are attributed to the interplay between the strongly coupled layers and substrate-driven perturbation, which can provide a new insight into the dimensional crossover of strongly coupled layered materials with hidden electronic phases.

Comprehensive understanding of iron-catalyzed Fischer–Tropsch synthesis product distribution with extensive reliable data

By integrating state-of-the-art characterization techniques, the work provided a more comprehensive perspective on FTS product distribution.

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.

When Molecular Dimerization Induces Magnetic Bi‐Stability at the Metal–Organic Interface (Adv. Phys. Res. 1/2023)

Molecular Dimers with Induced Magnetic Bi-Stability In article number 2200005, Jean-Pierre Bucher and co-workers present an on-surface assembly method to create metal–organic dimer complexes. Their method, which uses low-temperature scanning tunneling microscopy and spectroscopy, represents an experimental route towards dimer-based materials with complex magnetic structures. These materials could find future applications in spintronics, logics, and computing.

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.

A sacrificial magnet concept for field dependent surface science studies

We demonstrate a straightforward approach to integrating a magnetic field into a low-temperature scanning tunneling microscope (STM) by adhering an NdFeB permanent magnet to a magnetizable sample plate. To render our magnet concept compatible with high-temperature sample cleaning procedures, we make the irreversible demagnetization of the magnet a central part of our preparation cycle. After sacrificing the magnet by heating it above its Curie temperature, we use a transfer tool to attach a new magnet in-situ prior to transferring the sample into the STM. We characterize the magnetic field created by the magnet using the Abrikosov vortex lattice of superconducting NbSe2. Excellent agreement between the distance dependent magnetic fields from experiments and simulations allows us to predict the magnitude and orientation of magnetic flux at any location with respect to the magnet and the sample plate. Our concept is an accessible solution for field-dependent surface science studies that require fields in the range of up to 400 mT and otherwise detrimental heating procedures.•Accessible magnetic field generation.•Selectable field strength and orientation.•Compatible with high-temperature sample preparation.

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.

Study of the Cu(111) Surface by Scanning Tunneling Microscopy: The Morphology Evolution, Reconstructions, Superstructures and Line Defects.

The Cu(111) surface is an important substrate for catalysis and the growth of 2D materials, but a comprehensive understanding of the preparation and formation of well-ordered and atomically clean Cu(111) surfaces is still lacking. In this work, the morphology and structure changes of the Cu(111) surface after treatment by ion bombardment and annealing with a temperature range of 300-720 °C are investigated systematically by using in situ low-temperature scanning tunneling microscopy. With the increase of annealing temperature, the surface morphology changes from corrugation to straight edge, the number of screw dislocations changes from none to numerous, and the surface atomic structure changes from disordered to ordered structures (with many reconstructions). In addition, the changing trend of step width and step height in different stages is different (first increased and then decreased). A perfect Cu(111) surface with a step height of one atom layer (0.21 nm) and a width of more than 150 nm was obtained. In addition, two interesting superstructures and a new surface phase with a large number of line defects were found. This work serves as a strong foundation for understanding the properties of Cu(111) surface, and it also provides important guidance for the effective pretreatment of Cu(111) substrates, which are widely used.

Controlling the Spin States of FeTBrPP on Au(111).

Spin-flip excitations of iron porphyrin molecules on Au(111) are investigated with a low-temperature scanning tunneling microscope. The molecules adopt two distinct adsorption configurations on the surface that exhibit different magnetic anisotropy energies. Density functional theory calculations show that the different structures and excitation energies reflect unlike occupations of the Fe 3d levels. We demonstrate that the magnetic anisotropy energy can be controlled by changing the adsorption site, the orientation, or the tip-molecule distance.

Selective Activation of Aromatic C-H Bonds Catalyzed by Single Gold Atoms at Room Temperature.

Selective activation and controlled functionalization of C-H bonds in organic molecules is one of the most desirable processes in synthetic chemistry. Despite progress in heterogeneous catalysis using metal surfaces, this goal remains challenging due to the stability of C-H bonds and their ubiquity in precursor molecules, hampering regioselectivity. Here, we examine the interaction between 9,10-dicyanoanthracene (DCA) molecules and Au adatoms on a Ag(111) surface at room temperature (RT). Characterization via low-temperature scanning tunneling microscopy, spectroscopy, and noncontact atomic force microscopy, supported by theoretical calculations, revealed the formation of organometallic DCA-Au-DCA dimers, where C atoms at the ends of the anthracene moieties are bonded covalently to single Au atoms. The formation of this organometallic compound is initiated by a regioselective cleaving of C-H bonds at RT. Hybrid quantum mechanics/molecular mechanics calculations show that this regioselective C-H bond cleaving is enabled by an intermediate metal-organic complex which significantly reduces the dissociation barrier of a specific C-H bond. Harnessing the catalytic activity of single metal atoms, this regioselective on-surface C-H activation reaction at RT offers promising routes for future synthesis of functional organic and organometallic materials.

The composition and structure of the ubiquitous hydrocarbon contamination on van der Waals materials

The behavior of single layer van der Waals (vdW) materials is profoundly influenced by the immediate atomic environment at their surface, a prime example being the myriad of emergent properties in artificial heterostructures. Equally significant are adsorbates deposited onto their surface from ambient. While vdW interfaces are well understood, our knowledge regarding atmospheric contamination is severely limited. Here we show that the common ambient contamination on the surface of: graphene, graphite, hBN and MoS2 is composed of a self-organized molecular layer, which forms during a few days of ambient exposure. Using low-temperature STM measurements we image the atomic structure of this adlayer and in combination with infrared spectroscopy identify the contaminant molecules as normal alkanes with lengths of 20-26 carbon atoms. Through its ability to self-organize, the alkane layer displaces the manifold other airborne contaminant species, capping the surface of vdW materials and possibly dominating their interaction with the environment.

Enhanced Atomic Precision Fabrication by Adsorption of Phosphine into Engineered Dangling Bonds on H-Si Using STM and DFT.

The doping of Si using the scanning probe hydrogen depassivation lithography technique has been shown to enable placing and positioning small numbers of P atoms with nanometer accuracy. Several groups have now used this capability to build devices that exhibit desired quantum behavior determined by their atomistic details. What remains elusive, however, is the ability to control the precise number of atoms placed at a chosen site with 100% yield, thereby limiting the complexity and degree of perfection achievable. As an important step toward precise control of dopant number, we explore the adsorption of the P precursor molecule, phosphine, into atomically perfect dangling bond patches of intentionally varied size consisting of three adjacent Si dimers along a dimer row, two adjacent dimers, and one single dimer. Using low temperature scanning tunneling microscopy, we identify the adsorption products by generating and comparing to a catalog of simulated images, explore atomic manipulation after adsorption in select cases, and follow up with incorporation of P into the substrate. For one-dimer patches, we demonstrate that manipulation of the adsorbed species leads to single P incorporation in 12 out of 12 attempts. Based on the observations made in this study, we propose this one-dimer patch method as a robust approach that can be used to fabricate devices where it is ensured that each site of interest has exactly one P atom.

Adsorption structures of catechol on the ZnO(10-10) surface

The details of catechol interacting with the ZnO surfaces are critical for understanding how the organic chromophores anchor on and hence functionalize the ZnO materials. In this work, we apply low-temperature scanning tunneling microscopy (LT-STM) in combination with density functional theory (DFT) calculations to investigate the adsorption state and interface charge transfer of catechol on a ZnO(10-10) surface. For the molecules deposited at liquid nitrogen temperature, the fully-protonated (FP) status prevails in the isolated molecules despite the synergistic formation of half-protonated (HP) and fully-deprotonated (FD) ones. However, annealing to elevated temperature drives all the molecules to assemble into either linear or a c(2 × 2) superstructure composed of only FD catechols. Such spontaneous deprotonation of catechol is different from the predicted water-assisted process and plays critical roles in switching the catechol from electron acceptors to electron donors relative to the ZnO surface. These results may bring new insights into the design of optoelectronic and biomedical applications of the ZnO-organic compositional system.

Two-dimensional tellurium superstructures on Au(111) surfaces.

Two-dimensional (2D) allotropes of tellurium (Te), recently coined as tellurene, are currently an emerging topic of materials research due to the theoretically predicted exotic properties of Te in its ultrathin form and at the single atomic layer limit. However, a prerequisite for the production of such new and single elemental 2D materials is the development of simple and robust fabrication methods. In the present work, we report three different 2D superstructures of Te on Au(111) surfaces by following an alternative experimental deposition approach. We have investigated the superstructures using low-temperature scanning tunneling microscopy and spectroscopy, Auger electron spectroscopy (AES), and field emission AES. Three superstructures (13 × 13, 8 × 4, and √11 × √11) of 2D Te are observed in our experiments, and the formation of these superstructures is accompanied by the lifting of the characteristic 23 × √3 surface reconstruction of the Au(111) surface. Scanning tunneling spectroscopy reveals a strong dependence of the local electronic properties on the structural arrangement of the Te atoms on the Au(111) support, and we observe superstructure-dependent electronic resonances around the Fermi level and below the Au(111) conduction band. In addition to the appearance of the new electronic resonances, the emergence of band gaps with a p-type charge character has been evidenced for two out of three Te superstructures (13 × 13 and √11 × √11) on the Au(111) support.

Enhanced reducibility of well-defined Cr oxide nanostructures on Au(111) through Zn doping

Mixed oxides play important roles in many heterogeneous catalytic processes, and understanding of interaction between different oxide components is crucial for synthesizing the catalysts with high performances. Here, we introduce trace of metallic Zn species into well-defined chromium oxide (Cr oxide) nanostructures grown on Au(111) including CrO2-bilayer nanoislands and Cr2O7dinuclear clusters and study the impact of the dopant on reducibility of the Cr oxides. Combining low-temperature scanning tunneling microscopy (LT-STM) and X-ray photoelectron spectroscopy (XPS), we demonstrate that incorporation of 2.5 at.% Zn can lower the initial reduction temperature of Cr oxides by 70–160 K upon heating in ultrahigh vacuum. The reduction degree of Zn-doped Cr oxide is much larger than the pure oxide at the same heating temperature. Density functional theory (DFT) calculations reveal that the enhanced reducibility of the pristine oxide via introduction of Zn dopant mainly comes from the promoted activity of oxygen atoms due to Zn substitution of surface Cr.

Surface Characterization of the Solution‐Processed Organic–Inorganic Hybrid Perovskite Thin Films

The surface properties of organic-inorganic hybrid perovskites can strongly affect the efficiency and stability of corresponding devices. Even though different surface passivation methods are developed, the microscopic structures of solution-processed perovskite film surfaces are not systematically studied. This study uses low-temperature scanning tunneling microscopy to study the organic-inorganic hybrid perovskite thin films, MA0.4 FA0.6 PbI3 and MAPbI3 , synthesized by the spin-coating method.Flat surface structures, atomic steps, and crystal grain boundaries are resolved at an atomic resolution. The surface imperfections are also characterized, as well as the dominant defects.Simulations on different types of iodine vacancy configurations are performed by density functional theory calculations.In addition, it is observed that the surface iodine lattice structure is unstable during scanning. Tip scanning can also cause the vertical migration of surface iodine ions. The measurements provide the direct visualizations of the surface imperfections of the solution-processed perovskite films. They are essential for understanding the surface-related optoelectronic effects and rationally designing more efficient surface passivation methods.

Percolative superconductivity in electron-doped Sr1−xEuxCuO2+y films

Electron-doped infinite-layer Sr$_{1-x}$Eu$_{x}$CuO$_{2+y}$ films over a wide doping range have been prepared epitaxially on SrTiO$_3$(001) using reactive molecular beam epitaxy. In-plane transport measurements of the single crystalline samples reveal a dome-shaped nodeless superconducting phase centered at $x$ $\sim$ 0.15, a Fermi-liquid behavior and pronounced upturn in low temperature resistivity. We show that the resistivity upturn follows square-root temperature dependence, suggesting the emergence of superconductivity via a three-dimensional percolation process. The percolative superconductivity is corroborated spectroscopically by imaging the electronic phase separation between superconducting and metallic phases with low-temperature scanning tunneling microscopy. Furthermore, we visualize interstitial and apical oxygen anions that rapidly increase in number as $x>$ 0.12, and elucidate their impacts on the superconductivity and normal-state resistivity.

On-Surface Synthesis and Spectroscopy of Aluminum Phthalocyanine on Superconducting Lead.

Large ordered islands of aluminum phthalocyanine (AlPc) molecules, which are unstable in air, are synthesized from ClAlPc on Pb(100) via dechlorination. Low-temperature scanning tunneling microscopy reveals that isolated AlPc molecules lose their spin moment on superconducting Pb(100). Molecular magnetism, which is detected via Yu-Shiba-Rusinov (YSR) resonances, may be restored by surrounding a molecule with an array of neighbor molecules in artificial arrays or in a self-assembled monolayer. Unlike phthalocyanine (H2Pc) or lead phthalocyanine (PbPc) monolayers, where the YSR energy was found to depend strongly on the detailed configuration of the neighboring molecules, we find a similar magnetic moment on every second molecule for AlPc. In addition, YSR resonances lead to unusually high conductance peaks that are due to vibrational excitations. Twelve vibrational modes are resolved and discussed with respect to similar results from PbPc. The enhancement of the inelastic transitions is tentatively attributed to the large amplitude of the YSR resonances and the long lifetime of electrons in the molecular bound state. By assembling neighboring molecules into configurations that differ from those of the monolayer, the YSR energy may be fine-tuned, and a simple spin-state switching device is constructed.