Externally-triggerable optical pump-probe scanning tunneling microscopy with a time resoloution of tens-picosecond.

Photoinduced carrier dynamics of nanostructures play a crucial role in developing novel functionalities in advanced materials. Optical pump-probe scanning tunneling microscopy (OPP-STM) represents distinctive capabilities of real-space imaging of such carrier dynamics with nanoscale spatial resolution. However, combining the advanced technology of ultrafast pulsed lasers with STM for stable time-resolved measurements has remained challenging. The recent OPP-STM system, whose laser-pulse timing is electrically controlled by external triggers, has significantly simplified this combination but limited its application due to nanosecond temporal resolution. Here we report an externally-triggerable OPP-STM system with a temporal resolution in the tens-picosecond range. We also realize the stable laser illumination of the tip-sample junction by placing a position-movable aspheric lens driven by piezo actuators directly on the STM stage and by employing an optical beam stabilization system. We demonstrate the OPP-STM measurements on GaAs(110) surfaces, observing carrier dynamics with a decay time of [Formula: see text] ps and revealing local carrier dynamics at features including a step edge and a nanoscale defect. The stable OPP-STM measurements with the tens-picosecond resolution by the electrical control of laser pulses highlight the potential capabilities of this system for investigating nanoscale carrier dynamics of a wide range of functional materials.

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

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

Ultrathin Bismuth Film on High-Temperature Cuprate Superconductor Bi2Sr2CaCu2O8+δ as a Candidate of a Topological Superconductor.

One of the key challenges in condensed-matter physics is to establish a topological superconductor that hosts exotic Majorana fermions. Although various heterostructures consisting of conventional BCS (Bardeen-Cooper-Schrieffer) superconductors as well as doped topological insulators were intensively investigated, no conclusive evidence for Majorana fermions has been provided. This is mainly because of their very low superconducting transition temperatures ( Tc) and small superconducting-gap magnitude. Here, we report a possible realization of topological superconductivity at very high temperatures in a hybrid of Bi(110) ultrathin film and copper oxide superconductor Bi2Sr2CaCu2O8+δ (Bi2212). Using angle-resolved photoemission spectroscopy and scanning tunneling microscopy, we found that three-bilayer-thick Bi(110) on Bi2212 exhibits a proximity-effect-induced s-wave energy gap as large as 7.5 meV which persists up to Tc of Bi2212 (85 K). The small Fermi energy and strong spin-orbit coupling of Bi(110), together with the large pairing gap and high Tc, make this system a prime candidate for exploring stable Majorana fermions at very high temperatures.

Atomic-scale visualization of oxide thin-film surfaces.

The interfaces of complex oxide heterostructures exhibit intriguing phenomena not observed in their constituent materials. The oxide thin-film growth of such heterostructures has been successfully controlled with unit-cell precision; however, atomic-scale understandings of oxide thin-film surfaces and interfaces have remained insufficient. We examined, with atomic precision, the surface and electronic structures of oxide thin films and their growth processes using low-temperature scanning tunneling microscopy. Our results reveal that oxide thin-film surface structures are complicated in contrast to the general perception and that atomically ordered surfaces can be achieved with careful attention to the surface preparation. Such atomically ordered oxide thin-film surfaces offer great opportunities not only for investigating the microscopic origins of interfacial phenomena but also for exploring new surface phenomena and for studying the electronic states of complex oxides that are inaccessible using bulk samples.

Two distinct superconducting pairing states divided by the nematic end point in FeSe1-x S x.

Unconventional superconductivity often competes or coexists with other electronic orders. In iron-based superconductors, a central issue has been the relationship between superconductivity and electronic nematicity, spontaneous breaking of the lattice rotational symmetry. Using spectroscopic-imaging scanning tunneling microscopy, we simultaneously investigated the electronic structure and the superconducting gap in FeSe1-x S x , where the nematicity diminishes above the nematic end point (NEP) at x = 0.17. The nematic band structure appears as anisotropic quasiparticle-interference patterns that gradually become isotropic with increasing x without anomalies at the NEP. By contrast, the superconducting gap, which is intact in the nematic phase, discontinuously shrinks above the NEP. This implies that the presence or absence of nematicity results in two distinct pairing states, whereas the pairing interaction is insensitive to the strength of nematicity.

A Single-Atom-Thick TiO2 Nanomesh on an Insulating Oxide.

The electronic structures and macroscopic functionalities of two-dimensional (2D) materials are often controlled according to their size, atomic structures, and associated defects. This controllability is particularly important in ultrathin 2D nanosheets of transition-metal oxides because these materials exhibit extraordinary multifunctionalities that cannot be realized in their bulk constituents. To expand the variety of materials with exotic properties that can be used in 2D transition-metal-oxide nanosheets, it is essential to investigate fabrication processes for 2D materials. However, it remains challenging to fabricate such 2D nanosheets, as they are often forbidden because of the crystal structure and nature of their host oxides. In this study, we demonstrate the synthesis of a single-atom-thick TiO2 2D nanosheet with a periodic array of holes, that is, a TiO2 nanomesh, by depositing a LaAlO3 thin film on a SrTiO3(001)-(√13×√13)-R33.7° reconstructed substrate. In-depth investigations of the detailed structures, local density of states, and Ti valency of the TiO2 nanomesh using scanning tunneling microscopy/spectroscopy, scanning transmission electron microscopy, and density functional theory calculations reveal an unexpected upward migration of the Ti atoms of the substrate surface onto the LaAlO3 surface. These results indicate that the truncated TiO5 octahedra on the surface of perovskite oxides are very stable, leading to semiconducting TiO2 nanomesh formation. This nanomesh material can be potentially used to control the physical and chemical properties of the surfaces of perovskite oxides. Furthermore, this study provides an avenue for building functional atomic-scale oxide 2D structures and reveals the thin-film growth processes of complex oxides.

Charge-density wave in Ca-intercalated bilayer graphene induced by commensurate lattice matching.

We report the emergence of a charge-density wave (CDW) in Ca-intercalated bilayer graphene (C_{6}CaC_{6}), the thinnest limit of superconducting C_{6}Ca, observed by low-temperature, high-magnetic-field scanning tunneling microscopy or spectroscopy, and angle-resolved photoemission spectroscopy. While the possible superconductivity was not observed in epitaxially grown C_{6}CaC_{6} on a SiC substrate, a CDW order different from that observed on the surface of bulk C_{6}Ca was observed. It is inferred that the CDW state is induced by the potential modulation due to the commensurate lattice matching between the C_{6}CaC_{6} film and the SiC substrate.

Imaging the evolution of d states at a strontium titanate surface.

Oxide electronics is a promising alternative to the conventional silicon-based semiconductor technology, owing to the rich functionalities of oxide thin films and heterostructures. In contrast to the silicon surface, however, the electronic structure of the SrTiO3 surface, the most important substrate for oxide thin films growth, is not yet completely understood. Here we report on the electronic states of a reconstructed (001) surface of SrTiO3 determined in real space, with scanning tunneling microscopy/spectroscopy and density functional theory calculations. We found a remarkable energy dependence of the spectroscopic image: Theoretical analysis reveals that symmetry breaking at the surface lifts the degeneracy in the t2g state (dxy, dyz, and dzx) of Ti 3d orbitals, whose anisotropic spatial distribution leads to a sharp transition in the spectroscopic image as a function of energy. The knowledge obtained here could be used to gain further insights into emergent phenomena at the surfaces and interfaces with SrTiO3.

Scanning tunneling microscopy/spectroscopy on perovskite oxide thin films deposited in situ.

Complex oxide surfaces and interfaces, consisting of two or more cations and oxygen anions, have attracted a great deal of attention because their properties are crucial factors in the performance of catalysts, fuel cells, and Li-ion batteries. However, atomic-scale investigations of these oxide surfaces have been hindered because of the difficulties in surface preparation. Here, we demonstrate atomic-scale surface studies of complex perovskite oxides and the initial growth processes in oxide epitaxial films deposited on (✓13 × âœ“13)-R33.7° reconstructed SrTiO3 (001) substrates using a scanning tunneling microscope integrated with a pulsed laser deposition system. The atomically ordered, reconstructed SrTiO3 (001) surface is stable under the typical conditions necessary for the growth of oxide thin films, and hence is considered suitable for the study of the initial growth processes in oxide films. The atomic-scale microscopic/spectroscopic characterizations performed here shed light on the microscopic origin of electronic properties observed in complex oxides and their heterostructures.

Bottom-up graphene-nanoribbon fabrication reveals chiral edges and enantioselectivity.

We produce precise chiral-edge graphene nanoribbons on Cu{111} using self-assembly and surface-directed chemical reactions. We show that, using specific properties of the substrate, we can change the edge conformation of the nanoribbons, segregate their adsorption chiralities, and restrict their growth directions at low surface coverage. By elucidating the molecular-assembly mechanism, we demonstrate that our method constitutes an alternative bottom-up strategy toward synthesizing defect-free zigzag-edge graphene nanoribbons.

Visualizing atomistic formation process of SrOx thin films on SrTiO3.

Metallic conductivity observed in the heterostructure of LaAlO3/SrTiO3 has attracted great attention, triggering a debate over whether the origin is an intrinsic electronic effect or a defect-related phenomenon. One of the issues to be solved is the role of SrO layer, which turns the conductive interface into an insulator when inserted between LaAlO3 and SrTiO3. To understand the origins of this oxide interface phenomenon and to further explore unconventional functionalities, it is necessary to elucidate how SrO layers are formed during the initial growth process at the atomic level. Here, we atomically resolve growth processes of heteroepitaxial SrOx films on SrTiO3(001)-(√13×√13)-R33.7° substrate using scanning tunneling microscopy/spectroscopy. On the sub-unit-cell SrOx film surface, no periodic structure was observed as a result of random Ti incorporation into the SrOx islands, indicating the importance of the control of excess Ti atoms on the substrate prior to deposition. This random arrangement of Ti atoms is a marked contrast to the homoepitaxy on SrTiO3(001)-(√13×√13)-R33.7°. Furthermore, the formation of SrOx islands introduced defects in the surrounding SrTiO3 substrate surface. Such atom-by-atom engineering and characterizations of oxide heterostructures not only provide microscopic understanding of formation process of interfaces in metal-oxides, but also would lead to the creation of exotic electronic phenomena and novel functionalities at these interfaces.

Ca intercalated bilayer graphene as a thinnest limit of superconducting C6Ca.

Success in isolating a 2D graphene sheet from bulky graphite has triggered intensive studies of its physical properties as well as its application in devices. Graphite intercalation compounds (GICs) have provided a platform of exotic quantum phenomena such as superconductivity, but it is unclear whether such intercalation is feasible in the thinnest 2D limit (i.e., bilayer graphene). Here we report a unique experimental realization of 2D GIC, by fabricating calcium-intercalated bilayer graphene C(6)CaC(6) on silicon carbide. We have investigated the structure and electronic states by scanning tunneling microscopy and angle-resolved photoemission spectroscopy. We observed a free-electron-like interlayer band at the Brillouin-zone center, which is thought to be responsible for the superconductivity in 3D GICs, in addition to a large π* Fermi surface at the zone boundary. The present success in fabricating Ca-intercalated bilayer graphene would open a promising route to search for other 2D superconductors as well as to explore its application in devices.

Atomic-scale visualization of initial growth of homoepitaxial SrTiO3 thin film on an atomically ordered substrate.

The initial homoepitaxial growth of SrTiO(3) on a (√13 × âˆš13)-R33.7° SrTiO(3)(001) substrate surface, which can be prepared under oxide growth conditions, is atomically resolved by scanning tunneling microscopy. The identical (√13 × âˆš13) atomic structure is clearly visualized on the deposited SrTiO(3) film surface as well as on the substrate. This result indicates the transfer of the topmost Ti-rich (√13 × âˆš13) structure to the film surface and atomic-scale coherent epitaxy at the film/substrate interface. Such atomically ordered SrTiO(3) substrates can be applied to the fabrication of atom-by-atom controlled oxide epitaxial films and heterostructures.

Systematic analyses of vibration noise of a vibration isolation system for high-resolution scanning tunneling microscopes.

We designed and constructed an effective vibration isolation system for stable scanning tunneling microscopy measurements using a separate foundation and two vibration isolation stages (i.e., a combination of passive and active vibration isolation dampers). Systematic analyses of vibration data along the horizontal and vertical directions are present, including the vibration transfer functions of each stage and the overall vibration isolation system. To demonstrate the performance of the system, tunneling current noise measurements are conducted with and without the vibration isolation. Combining passive and active vibration isolation dampers successfully removes most of the vibration noise in the tunneling current up to 100 Hz. These comprehensive vibration noise data, along with details of the entire system, can be used to establish a clear guideline for building an effective vibration isolation system for various scanning probe microscopes and electron microscopes.