Low-temperature Scanning Tunneling Microscopy Research Articles

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.

Dynamic bonding influenced by the proximity of adatoms to one atom high step edges

Low-temperature scanning tunneling microscopy is used here to study dynamic bonding of gold atoms on surfaces under low coordination conditions. In the experiments, using an atomically-sharp gold tip, a gold adatom is deposited onto a gold surface with atomic precision either on the first hollow site near a step edge, or far away from it. Classical molecular dynamics simulations at 4.2 K and density functional theory calculations serve to elucidate the difference in the bonding behavior between these two different placements, while also providing information on the crystalline classification of the STM tips based on their experimental performance.

Observation of robust zero-energy state and enhanced superconducting gap in a trilayer heterostructure of MnTe/Bi2Te3/Fe(Te, Se).

The interface between magnetic material and superconductors has long been predicted to host unconventional superconductivity, such as spin-triplet pairing and topological nontrivial pairing state, particularly when spin-orbital coupling (SOC) is incorporated. To identify these unconventional pairing states, fabricating homogenous heterostructures that contain such various properties are preferred but often challenging. Here, we synthesized a trilayer-type van der Waals heterostructure of MnTe/Bi2Te3/Fe(Te, Se), which combined s-wave superconductivity, thickness-dependent magnetism, and strong SOC. Via low-temperature scanning tunneling microscopy, we observed robust zero-energy states with notably nontrivial properties and an enhanced superconducting gap size on single unit cell (UC) MnTe surface. In contrast, no zero-energy state was observed on 2-UC MnTe. First-principle calculations further suggest that the 1-UC MnTe has large interfacial Dzyaloshinskii-Moriya interaction and a frustrated AFM state, which could promote noncolinear spin textures. It thus provides a promising platform for exploring topological nontrivial superconductivity.

Planar bridging an atomically precise surface trench with a single molecular wire on an Au(1 1 1) surface

In a bridge configuration, a single graphene nanoribbon (GNR) is positioned with a picometer precision over a trench in between two monoatomic steps on an Au(111) surface. This GNR molecular wire adopts a deformed conformation towards the down terrace in between the two contact step edges. Using differential conductance dI/dV mapping from a low-temperature scanning tunneling microscope, it is demonstrated how the electronic delocalization along GNR is cut at each contact by its down curvature. It points out the need to bring conductive nanocontacts backside of the support for preserving the front side GNR planar conformation.

Spin-related electronic pathway through single molecule on Au(111)

Spin properties of organic molecules have attracted great interest for their potential applications in spintronic devices and quantum computing. Fe-tetraphenyl porphyrin (FeTPP) is of particular interest for its robust magnetic properties on metallic substrates. FeTPP is prepared in vacuum via on-surface synthesis. Molecular structure and spin-related transport properties are characterized by low-temperature scanning tunneling microscope and spectroscopy at 0.5 K. Density functional theory calculations are performed to understand molecular adsorption and spin distribution on Au(111). The molecular structure of FeTPP is distorted upon adsorption on the substrate. Spin excitations of FeTPP are observed on the Fe atom and high pyrrole groups in differential conductance spectra. The calculated spin density distribution indicates that the electron spin of FeTPP is mainly distributed on the Fe atom. The atomic transmission calculation indicates that electrons transport to substrate is mediated through Fe atom, when the tip is above the high pyrrole group.

Direct observation of multiband charge density waves in NbTe2

The electronic structure of periodic lattice distortion (PLD) in ${\mathrm{NbTe}}_{2}$ was examined using low-temperature scanning tunneling spectroscopy and microscopy. The striped PLDs with $3\ifmmode\times\else\texttimes\fi{}1$ and $1\ifmmode\times\else\texttimes\fi{}\frac{9}{2}$ superstructures were characterized in real and reciprocal space. The simultaneous formation of momentum-specific suppressions in the spectral weight and phase shifts of the wavefront related to the superstructures were observed at multiple energies. These unusual energy dependencies are well agreed with the charge density waves (CDWs) formed in the multiband electronic structure of ${\mathrm{NbTe}}_{2}$. Fermi-surface nesting and reconstruction of the reciprocal lattice were suggested in developing the multiband CDWs in ${\mathrm{NbTe}}_{2}$.

Precise Synthesis of Concentric Ring, Helicoid, and Ladder Metallo-Polymers with Chevron-Shaped Monomers.

Molecular geometry represents one of the most important structural features and governs physical properties and functions of materials. Nature creates a wide array of substances with distinct geometries but similar chemical composition with superior efficiency and precision. However, it remains a formidable challenge to construct abiological macromolecules with various geometries based on identical repeating units, owing to the lack of corresponding synthetic approaches for precisely manipulating the connectivity between monomers and feasible techniques for characterizing macromolecules at the single-molecule level. Herein, we design and synthesize a series of tetratopic monomers with chevron stripe shape which serve as the key precursors to produce four distinct types of metallo-macromolecules with well-defined geometries, viz., the concentric hexagon, helicoid polymer, ladder polymer, and cross-linked polymer, via platinum-acetylide couplings. Concentric hexagon, helicoid, and ladder metallo-polymers are directly visualized by transmission electron microscopy, atomic force microscopy, and ultra-high-vacuum low-temperature scanning tunneling microscopy at the single-molecule level. Finally, single-walled carbon nanotubes (SWCNTs) are selected as the guest to investigate the structure-property relationship based on such macromolecules, among which the helicoid metallo-polymer shows high efficiency in wrapping SWCNTs with geometry-dependent selectivity.

Negative Differential Resistance in Spin-Crossover Molecular Devices.

We demonstrate, based on low-temperature scanning tunneling microscopy (STM) and spectroscopy, a pronounced negative differential resistance (NDR) in spin-crossover (SCO) molecular devices, where a FeII SCO molecule is deposited on surfaces. The STM measurements reveal that the NDR is robust with respect to substrate materials, temperature, and the number of SCO layers. This indicates that the NDR is intrinsically related to the electronic structure of the SCO molecule. Experimental results are supported by density functional theory (DFT) with nonequilibrium Green's function (NEGF) calculations and a generic theoretical model. While the DFT+NEGF calculations reproduce NDR for a special atomically sharp STM tip, the effect is attributed to the energy-dependent tip density of states rather than the molecule itself. We, therefore, propose a Coulomb blockade model involving three molecular orbitals with very different spatial localization as suggested by the molecular electronic structure.

Enhanced photon emission by field emission resonances and local surface plasmon in tunneling junction

We investigated the photon emission spectra on Ag (111) surface excited by tunneling electrons using a low temperature scanning tunneling microscope in ultrahigh vacuum. Characteristic plasmon modes were illustrated as a function of the bias voltage. The one electron excitation process was revealed by the linear relationship between the luminescence intensity and the tunneling current. Luminescence enhancement is observed in the tunneling regime for the relatively high bias voltages, as well as at the field emission resonance with bias voltage increased up to 9 V. Presence of a silver (Ag) nanoparticle in the tunneling junction results in an abnormally strong photon emission at the high field emission resonances, which is explained by the further enhancement due to coupling between the localized surface plasmon and the vacuum. The results are of potential value for applications where ultimate enhancement of photon emission is desired.

Ubiquitous stripe phase and enhanced electron pairing in the interfacial high- Tc superconductor FeSe/BaTiO3

Monolayer FeSe grown on SrTiO$_3$ provides a new playground for high-Tc superconductivity. A recent study shows the importance of stripy instability for superconductivity enhancement in FeSe/SrTiO3. However, it is still under debate whether such a stripe phase is ubiquitously bound to the interfacial superconductivity. Here, we report on molecular beam epitaxy growth and low-temperature scanning tunneling microscopy study of FeSe films on BaTiO$_3$(001). We find that the stripe phase is more prominent in FeSe/BaTiO$_3$. Long-range stripes exist in bilayer and triple-layer FeSe films at 4 K and even persist up to 77 K in the case of bilayer FeSe, with enlarged superconducting gaps upon alkali-metal deposition. The results point out an intimate correlation between the interfacial superconductivity and the stripe phase.

Fully Two-Dimensional Incommensurate Charge Modulation on the Pd-Terminated Polar Surface of PdCoO2.

Here, we use low-temperature scanning tunneling microscopy and spectroscopy to study the polar surfaces of PdCoO2. On the CoO2-terminated polar surface, we detect the quasiparticle interference pattern originating from the Rashba-like spin-split surface states. On the well-ordered Pd-terminated polar surface, we observe a regular lattice that has a larger lattice constant than the atomic lattice of PdCoO2. In comparison with the shape of the hexagonal Fermi surface on the Pd-terminated surface, we identify this regular lattice as a fully two-dimensional incommensurate charge modulation that is driven by the Fermi surface nesting. More interestingly, we also find the moiré pattern induced by the interference between the two-dimensional incommensurate charge modulation in the Pd layer and its atomic lattice. Our results not only show a new charge modulation on the Pd surface of PdCoO2 but also pave the way for fully understanding the novel electronic properties of this material.

(Invited) Development of THz-Field-Driven Scanning Tunneling Luminescence Spectroscopy for Future Investigation of Exciton Dynamics

Exciton dynamics is responsible for the photophysical and photochemical functions, such as energy harvesting, light emission, and photosynthesis. In particular, energy conversions, transfers, and dissipations at interfaces and nanostructures govern the dynamics of excitons. Nevertheless, the spatial resolutions of conventional optical methods are limited to several hundred nanometers due to the diffraction limit of light. Luminescence measurements combined with scanning tunneling microscopy (STM) enable to investigate optical properties with sub-nanometer spatial resolution in various systems such as metals[1], semiconductors[2], 2D materials[3], and molecules[4-5]. In this method, the scanning tunneling luminescence (STL) spectroscopy, photons induced by the tunneling current of STM are detected. Since the tunneling current can be controlled with atomic spatial resolution, it is possible to investigate optical phenomena in localized regions. While STL spectroscopy is a powerful tool for investigating exciton dynamics with atomic-scale spatial resolution, the time resolution of STL spectroscopy is limited because it uses “steady-state” tunneling current for the excitation. Therefore, this method cannot be applicable to track the ultrafast exciton dynamics in real-time.For overcoming the limitation of time resolution of STM, a single-cycle terahertz (THz) electric field has recently been installed to drive tunneling electrons[6-9]. By coupling the THz pulse to an atomically sharp metal tip of STM, the electric field is confined to the tip, and it enables to manipulate the tunneling electrons with extremely high spatiotemporal resolution. This method, THz-STM, has been utilized to track the ultrafast carrier dynamics[6-8] and motion of a molecule[9] with sub-picosecond time resolution. In this work, we combined a photon detection system with THz-STM to establish THz-STL spectroscopy (Fig. 1a). We measured visible photon emission from the radiative decay of a localized plasmon as the first demonstration of THz-STL spectroscopy[10]. We anticipate that the THz-STL spectroscopy will open new avenues for “real-time” and “real-space” investigations of exciton dynamics in near future.In this work, we generated single-cycle THz pulses via optical rectification of laser pulses from a Yb fiber laser in a LiNbO3 prism using a tilted-pulse-front configuration (Fig. 1b). The generated THz pulses were guided into a low-temperature STM and focused to the STM junction (Fig. 1a). Figure 1c shows a current trace on Ag(111) surface, where the current induced by the THz pulses was measured as 2.65 pA. Based on the simulation of electron tunneling probability, the maximum magnitude of the voltage applied by the THz pulse was estimated to be ~6.5 V. Figure 1d shows STL spectra when the THz pulse was either introduced to the STM (red) or blocked (grey). Whereas no peak is seen in the grey spectrum, a broad peak ranging from 1.3 eV to 2.3 eV appears in the red spectrum, which is originated from the radiative decay of a plasmon localized in the gap.In this presentation, we would like to discuss the detailed mechanism of plasmon excitation by THz-field-driven electrons as well as the challenges of applying THz-STL to the real-time investigation of exciton dynamics in a molecule.[1] R. Berndt et al., Phys. Rev. Lett. 67, 3796 (1991). [2] J. K. Gimzewski et al., Z. Phys. B Condensed Matter 72, 497 (1988). [3] Schuler et al., Sci. Adv. 6, eabb5988 (2020). [4] H. Imada et al., Nature 538, 364 (2016). [5] K. Kimura et al., Nature 570, 210 (2019). [6] T. L. Cocker et al., Nat. Photon. 7, 620 (2013). [7] K. Yoshioka et al., Nat. Photon. 10, 762 (2016). [8] V. Jelic et al., Nature Physics 13, 591 (2017). [9] D. Peller et al., Nature 585, 58 (2020). [10] K. Kimura et al., ACS photon. 8, 982 (2021). Figure 1

Real-Space Investigation of the Multiple Halogen Bonds by Ultrahigh-Resolution Scanning Probe Microscopy.

The chemical bond is of central interest in chemistry, and it is of significance to study the nature of intermolecular bonds in real-space. Herein, non-contact atomic force microscopy (nc-AFM) and low-temperature scanning tunneling microscopy (LT-STM) are employed to acquire real-space atomic information of molecular clusters, i.e., monomer, dimer, trimer, tetramer, formed on Au(111). The formation of the various molecular clusters is due to the diversity of halogen bonds. DFT calculation also suggests the formation of three distinct halogen bonds among the molecular clusters, which originates from the noncovalent interactions of Br-atoms with the positive potential H-atoms, neutral potential Br-atoms, and negative potential N-atoms, respectively. This work demonstrates the real-space investigation of the multiple halogen bonds by nc-AFM/LT-STM, indicating the potential use of this technique to study other intermolecular bonds and to understand complex supramolecular assemblies at the atomic/sub-molecular level.

Low-Dimensional Porous Carbon Networks Using Single-/Triple-Coupling Polycyclic Hydrocarbon Precursors.

Polycyclic hydrocarbons (PHs) share the same hexagonal structure of sp2 carbons as graphene but possess an energy gap due to quantum confinement effect. PHs can be synthesized by a bottom-up strategy starting from small building blocks covalently bonded into large 2D organic sheets. Further investigation of the role of the covalent bonding/coupling ways on their electronic properties is needed. Here, we demonstrate a surface-mediated synthesis of hexa-peri-hexabenzocoronene (HBC) and its extended HBC oligomers (dimers, trimers, and tetramers) via single- and triple-coupling ways and reveal the implication of different covalent bonding on their electronic properties. High-resolution low-temperature scanning tunneling microscopy and noncontact atomic force microscopy are employed to in situ determine the atomic structures of as-synthesized HBC oligomers. Scanning tunneling spectroscopy measurements show that the length extension of HBC oligomers narrows the energy gap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). Furthermore, the energy gaps of triple-coupling HBC oligomers are smaller and decrease more significantly than that of the single-coupling ones. We hypothesize that the triple coupling promotes a more effective delocalization of π-electrons than the single coupling, according to density functional theory calculations. We also demonstrate that the HBC oligomers can further extend across the substrate steps to achieve conjugated polymers and large-area porous carbon networks.

Melamine self-assembly and dehydrogenation on Ag(111) studied by tip-enhanced Raman spectroscopy

The adsorption and self-assembly structures of melamine molecules on an Ag(111) surface are studied by low temperature scanning tunneling microscopy (STM) combined with tip-enhanced Raman spectroscopy (TERS). Two ordered self-assembly phases of melamine molecules on Ag(111) were studied by STM and TERS, combining with first-principles simulations. The α-phase consists of flat-lying melamine molecules, while the β-phase consists of mixed up-standing/tilted melamine molecules. Moreover, dehydrogenation of melamine can be controlled by annealing the sample as well as by a tip-enhanced photo-catalytic effect. Our work demonstrates TERS as a powerful tool not only for investigating the configuration and vibration properties of molecules on a metal surface with high spatial resolution but also for manipulating the chemical reactions with tip and photo-induced effects.

Nontrivial Doping Evolution of Electronic Properties in Ising-Superconducting Alloys.

Transition metal dichalcogenides offer unprecedented versatility to engineer 2D materials with tailored properties to explore novel structural and electronic phase transitions. In this work, the atomic-scale evolution of the electronic ground state of a monolayer of Nb1- δ Moδ Se2 across the entire alloy composition range (0 < δ< 1) is investigated using low-temperature (300 mK) scanning tunneling microscopy and spectroscopy (STM/STS). In particular, the atomic and electronic structure of this 2D alloy throughout the metal to semiconductor transition (monolayer NbSe2 to MoSe2 ) is studied. The measurements enable extraction of the effective doping of Mo atoms, the bandgap evolution and the band shifts, which are monotonic with δ. Furthermore, it is demonstrated that collective electronic phases (charge density wave and superconductivity) are remarkably robust against disorder and further shown that the superconducting TC changes non-monotonically with doping. This contrasting behavior in the normal and superconducting state is explained using first-principles calculations. Mo doping is shown to decrease the density of states at the Fermi level and the magnitude of pair-breaking spin fluctuations as a function of Mo content. These results paint a detailed picture of the electronic structure evolution in 2D TMD alloys, which is of utmost relevance for future 2D materials design.

Topological Defects Induced High-Spin Quartet State in Truxene-Based Molecular Graphenoids

Topological Defects Induced High-Spin Quartet State in Truxene-Based Molecular Graphenoids

Self-assembled and crystalline films of rubrene grown on Cd(0001) surface

We investigated the 2D self-assembled thin films of rubrene molecules on metallic Cd(0001) surface using low-temperature scanning tunneling microscopy. The isolated rubrene molecules adsorbed on Cd(0001) surface exhibit chiral characteristics. Three self-assembled structures, zigzag chain, linear chain and dimerized chain, have been identified in rubrene monolayer. The zigzag chain resembles the a-c plane of the orthorhombic crystal. Furthermore, we found the monoclinic phase of rubrene crystals in the second rubrene layer, theoretically predicted but not experimentally confirmed. These results provide new choices and ideas for preparing a new rubrene light-emitting device.