Cryogenic Scanning Tunneling Microscope Research Articles

Quantitative Analogue Simulation of Planar Molecules.

Synthetic quantum systems provide a pathway for exploring the physics of complex quantum matter in a programmable fashion. This approach becomes particularly advantageous when it comes to systems that are thermodynamically unfavorable. By sculpting the potential landscape of Cu(111) surfaces with carbon monoxide quantum corrals in a cryogenic scanning tunneling microscope, we created analogue simulators of planar organic molecules, including antiaromatic and non-Kekulé species that are generally reactive or unstable. Spectroscopic imaging of such synthetic molecules reveals close replications of molecular orbitals obtained from ab initio calculations of the organic molecules. We further illustrate the quantitative nature of such analogue simulators by faithful extraction of bond orders and global aromaticity indices, which are otherwise technically daunting using real molecules. Our approach therefore sets the stage for new research frontiers pertaining to the quantum physics and chemistry of designer nanostructures.

Networks of Hydrogen Bond Networks in Water Clusters.

Water clusters play a prominent role in atmospheric and solution chemistry. Numerous arrangements of protons, H-bond configurations or networks, shape the cluster properties. Studies of small water clusters by cryogenic scanning tunneling microscopy and high-resolution rovibrational spectroscopy have established proton rearrangement mechanisms forming pathways between H-bond networks. The mechanisms, concerted tunneling in particular, describe the local processes connecting pairs of configurations. Here, proton rearrangement networks mapping these transformations are defined and explored to provide a global view of the H-bond configurations in clusters. The networks are constructed for clusters of different sizes and structures. Their analysis reveals an odd-even effect with respect to the number of water molecules, exponential growth of the small-world character, bimodality of the degree distributions, and gapped assortativity of the networks. The last two properties signify the unexpected division of H-bond configurations into two classes according to their network connectivity. The results demonstrate qualitative differences between proton rearrangement mechanisms, suggest a strong influence of the cluster structure. The generated networks are of interest as real-world models for network rewiring; they establish an alternative platform for studies of proton rearrangements in H-bonded systems.

Ambipolar Doping of Monolayer FeSe by Interface Engineering

We report on ambipolar modulation doping of monolayer FeSe epitaxial films grown by molecular beam epitaxy and in situ spectroscopic measurements via a cryogenic scanning tunneling microscopy. It is found that hole doping kills superconductivity in monolayer FeSe films on metallic Ir(001) substrates, whereas electron doping from polycrystalline IrO2/SrTiO3 substrate enhances significantly the superconductivity with an energy gap of 10.3 meV. By exploring substrate-dependent superconductivity, we elucidate the essential impact of substrate work functions on the superconductivity of monolayer FeSe films. Our results therefore offer a valuable reference guide for further enhancement of the transition temperature T c in FeSe-based superconductors by interface engineering.

Cryogenic spectroscopic imaging scanning tunnelling microscope in a water-cooled magnet down to 1.7 K

Spectroscopic-imaging scanning tunnelling microscope (SI-STM) in a water-cooled magnet (WM) at low temperature has long been desirable in the condensed matter physics area since it is crucial for addressing various scientific problems, such as the behaviour of Cooper electrons crossing Hc2 in a high-temperature superconductor. Here we report on the construction and performance of the first atomically resolved cryogenic SI-STM in a WM. It operates at low temperatures of down to 1.7 K and in magnetic fields of up to 22 T (the WM's upper safety limit). The WM-SI-STM unit features a high-stiffness sapphire-based frame with the lowest eigenfrequency being 16 kHz. A slender piezoelectric scan tube (PST) is coaxially embedded in and glued to the frame. A well-polished zirconia shaft is spring-clamped onto the gold-coated inner wall of the PST to serve both the stepper and the scanner. The microscope unit as a whole is elastically suspended in a tubular sample space inside a 1K-cryostat by a two-stage internal passive vibrational reduction system, achieving a base temperature below 2 K in a static exchange gas. We demonstrate the SI-STM by imaging TaS2 at 50 K and FeSe at 1.7 K. Detecting the well-defined superconducting gap of FeSe, an iron-based superconductor, at variable magnetic fields demonstrates the device's spectroscopic imaging capability. The maximum noise intensity at the typical frequency is 3 pA per square root Hz at 22 T, which is only slightly worse than at 0 T, indicating the insensitivity of the STM to harsh conditions. In addition, our work shows the potential of SI-STMs for use in a WM and hybrid magnet with a 50 mm-bore size where high fields can be generated.

Ultra-low-noise transimpedance amplifier in cryogenic STM for studying novel quantum states by measuring shot noise

An ultra-low-noise large-bandwidth transimpedance amplifier (TIA) for cryogenic scanning tunneling microscope (CryoSTM) is proposed. The TIA connected with the tip-sample component in CryoSTM is called as CryoSTM-TIA. Its transimpedance gain is as high as 1 GΩ, and its bandwidth is over 300 kHz, but its equivalent input noise current power spectral density is less than 4 (fA)2/Hz at 100 kHz. The low inherent noise for the CryoSTM-TIA is due to its special design: (1) its pre-amplifier is made of a pair of low-noise cryogenic high electron mobility transistors (HEMTs); (2) the noise generated by one HEMT is eliminated by a large capacitor; (3) the capacitance of the cable connected the gate of the other HEMT to the tip is minimized; (4) thermal noise sources, such as the feedback resistor, are placed in the cryogenic zone. The dc output voltage drift of the CryoSTM-TIA is very low, as 5 μV/°C. The apparatus can be used for measuring the scanning tunneling differential conductance spectra, especially the scanning tunneling shot noise spectra (STSNS) of quantum systems, even if the shot noise is very low. It provides a universal tool to study various novel quantum states by measuring STSNS, such as detecting the Majorana bound states.

Observation of Coulomb blockade and Coulomb staircases in superconducting Pr0.8Sr0.2NiO2 films

Motivated by the discovery of superconductivity in the infinite-layer nickelate family, we report an experimental endeavor to clean the surface of nickelate superconductor Pr0.8Sr0.2NiO2 films by Ar+ ion sputtering and subsequent annealing, and we study their electronic structures by cryogenic scanning tunneling microscopy and spectroscopy. The annealed surfaces are characterized by nano-sized clusters and Coulomb staircases with periodicity inversely proportional to the projected area of the nanoclusters, consistent with a double-barrier tunneling junction model. Moreover, the dynamical Coulomb blockade effects are observed and result in well-defined energy gaps around the Fermi level, which correlate closely with the specific configuration of the junctions. These Coulomb blockade-related phenomena provide an alternative plausible cause of the observed gap structure that should be considered in the spectroscopic understanding of nickelate superconductors with the nano-clustered surface.

A spectroscopic-imaging scanning tunneling microscope in vector magnetic field.

Cryogenic scanning tunneling microscopy and spectroscopy (STM/STS) performed in a high vector magnetic field provide unique possibilities for imaging surface magnetic structures and anisotropic superconductivity and exploring spin physics in quantum materials with atomic precision. Here, we describe the design, construction, and performance of a low-temperature, ultra-high-vacuum (UHV) spectroscopic-imaging STM equipped with a vector magnet capable of applying a field of up to 3T in any direction with respect to the sample surface. The STM head is housed in a fully bakeable UHV compatible cryogenic insert and is operational over variable temperatures ranging from ∼300 down to 1.5K. The insert can be easily upgraded using our home-designed 3He refrigerator. In addition to layered compounds, which can be cleaved at a temperature of either ∼300, ∼77, or ∼4.2 K to expose an atomically flat surface, thin films can also be studied by directly transferring using a UHV suitcase from our oxide thin-film laboratory. Samples can be treated further with a heater and a liquid helium/nitrogen cooling stage on a three-axis manipulator. The STM tips can be treated in vacuo by e-beam bombardment and ion sputtering. We demonstrate the successful operation of the STM with varying the magnetic field direction. Our facility provides a way to study materials in which magnetic anisotropy is a key factor in determining the electronic properties such as in topological semimetals and superconductors.

Atomic structures and interfacial engineering of ultrathin indium intercalated between graphene and a SiC substrate.

Two-dimensional metals stabilized at the interface between graphene and SiC are attracting considerable interest thanks to their intriguing physical properties, providing promising material platforms for quantum technologies. However, the nanoscale picture of the ultrathin metals within the interface that represents their ultimate two-dimensional limit has not been well captured. In this work, we explore the atomic structures and electronic properties of atomically thin indium intercalated at the epitaxial graphene/SiC interface by means of cryogenic scanning tunneling microscopy. Two types of surfaces with distinctive crystalline characteristics are found: (i) a triangular indium arrangement epitaxially matching the (√3 × √3)R30° cell of the SiC substrate and (ii) a featureless surface of more complex atomic structures. Local tunneling spectroscopy reveals a varying n-type doping in the graphene capping layer induced by the intercalated indium and an occupied electronic state at ∼-1.1 eV that is attributed to the electronic structure of the newly formed interface. Tip-induced surface manipulation is used to alter the interfacial landscape; indium atoms are locally de-intercalated below graphene. This enables the quantitative measurement of the intercalation thickness revealing mono and bi-atomic layer indium within the interface and offers the capability to tune the number of metal layers such that a monolayer is converted irreversibly to a bilayer indium. Our findings demonstrate a scanning probe-based method for in-depth investigation of ultrathin metal at the atomic level, holding importance from both fundamental and technical viewpoints.

Experimental observation of pseudogap in a modulation-doped Mott insulator: Sn/Si(111)-()R30°

Unusual quantum phenomena usually emerge upon doping Mott insulators. Using a molecular beam epitaxy system integrated with cryogenic scanning tunneling microscope, we investigate the electronic structure of a modulation-doped Mott insulator Sn/Si(111)-()R30°. In underdoped regions, we observe a universal pseudogap opening around the Fermi level, which changes little with the applied magnetic field and the occurrence of Sn vacancies. The pseudogap gets smeared out at elevated temperatures and alters in size with the spatial confinement of the Mott insulating phase. Our findings, along with the previously observed superconductivity at a higher doping level, are highly reminiscent of the electronic phase diagram in the doped copper oxide compounds.

Topological states in dimerized quantum-dot chains created by atom manipulation

Topological electronic phases exist in a variety of naturally occurring materials but can also be created artificially. We used a cryogenic scanning tunneling microscope to create dimerized chains of identical quantum dots on a semiconductor surface and to demonstrate that these chains give rise to one-dimensional topological phases. The dots were assembled from charged adatoms, creating a confining potential with single-atom precision acting on electrons in surface states of the semiconductor. Coupling between the dots leads to electronic states localized at the ends of the chains, as well as at deliberately created internal domain walls, in agreement with the predictions of the Su-Schrieffer-Heeger model. Scanning tunneling spectroscopy also reveals deviations from this well-established model manifested in an asymmetric level spectrum and energy shifts of the boundary states. The deviations arise because the dots are charged and hence lead to an onsite potential that varies along the chain. We show that this variation can be mitigated by electrostatic gating using auxiliary charged adatoms, enabling fine-tuning of the boundary states and control of their superposition. The experimental data, which are complemented by theoretical modeling of the potential and the resulting eigenstates, reveal the important role of electrostatics in these engineered quantum structures.

Electronic Quantum Materials Simulated with Artificial Model Lattices.

The band structure and electronic properties of a material are defined by the sort of elements, the atomic registry in the crystal, the dimensions, the presence of spin–orbit coupling, and the electronic interactions. In natural crystals, the interplay of these factors is difficult to unravel, since it is usually not possible to vary one of these factors in an independent way, keeping the others constant. In other words, a complete understanding of complex electronic materials remains challenging to date. The geometry of two- and one-dimensional crystals can be mimicked in artificial lattices. Moreover, geometries that do not exist in nature can be created for the sake of further insight. Such engineered artificial lattices can be better controlled and fine-tuned than natural crystals. This makes it easier to vary the lattice geometry, dimensions, spin–orbit coupling, and interactions independently from each other. Thus, engineering and characterization of artificial lattices can provide unique insights. In this Review, we focus on artificial lattices that are built atom-by-atom on atomically flat metals, using atomic manipulation in a scanning tunneling microscope. Cryogenic scanning tunneling microscopy allows for consecutive creation, microscopic characterization, and band-structure analysis by tunneling spectroscopy, amounting in the analogue quantum simulation of a given lattice type. We first review the physical elements of this method. We then discuss the creation and characterization of artificial atoms and molecules. For the lattices, we review works on honeycomb and Lieb lattices and lattices that result in crystalline topological insulators, such as the Kekulé and “breathing” kagome lattice. Geometric but nonperiodic structures such as electronic quasi-crystals and fractals are discussed as well. Finally, we consider the option to transfer the knowledge gained back to real materials, engineered by geometric patterning of semiconductor quantum wells.

Low-noise large-bandwidth transimpedance amplifier for measuring scanning tunneling shot noise spectra in cryogenic STM and its applications

Shot noise is a powerful tool to study quantum systems. In this work, a design of transimpedance amplifier (TIA) for a cryogenic scanning tunneling microscope (CryoSTM) is proposed to meet the requirements of the shot noise measurements for quantum systems. In the TIA, the preamplifier is made of the low-noise low-power cryogenic high electron mobility transistors. With the high transimpedance gain of 1 GΩ, the bandwidth of the proposed TIA is larger than 300 kHz. In the CryoSTM, the TIA with the tip-sample component is called as CryoSTM-TIA. The bandwidth of the proposed CryoSTM-TIA is still larger than 300 kHz. Its equivalent input noise current power spectral density is less than 30(fA)2/Hz at 100 kHz. It is detailed, for quantum systems, by using the CryoSTM-TIA, how to measure scanning tunneling current spectra, scanning tunneling differential conductance spectra, and scanning tunneling noise current power spectra, in atomic scale, and then extract their scanning tunneling shot noise spectra. Thus, it is possible to study novel quantum phenomena in various quantum systems by measuring shot noise with the CryoSTM-TIA, such as the Andreev reflection in atomic scale, the Kondo effect in a single molecular magnet, and the existence of Majorana bound states, etc.

Tunneling-tip-induced collapse of the charge gap in the excitonic insulator Ta2NiSe5

Tuning many-body electronic phases by an external handle is of both fundamental and practical importance in condensed matter science. The tunability mirrors the underlying interactions, and gigantic electric, optical and magnetic responses to minute external stimuli can be anticipated in the critical region of phase change. The excitonic insulator is one of the exotic phases of interacting electrons, produced by the Coulomb attraction between a small and equal number of electrons and holes, leading to the spontaneous formation of exciton pairs in narrow-gap semiconductors/semimetals. The layered chalcogenide Ta$_2$NiSe$_5$ has been recently discussed as such an excitonic insulator with an excitation gap of ~250 meV below $T_c$ = 328 K. Here, we demonstrate a drastic collapse of the excitation gap in Ta$_2$NiSe$_5$ and the realization of a zero-gap state by moving the tip of a cryogenic scanning tunneling microscope towards the sample surface by a few angstroms. The collapse strongly suggests the many-body nature of the gap in the insulating state of Ta$_2$NiSe$_5$, consistent with the formation of an excitonic state. We argue that the collapse of the gap is driven predominantly by the electrostatic charge accumulation at the surface induced by the proximity of the tip and the resultant carrier doping of the excitonic insulator. Our results establish a novel phase-change function based on excitonic insulators.

Moiré superlattice modulations in single-unit-cell FeTe films grown on NbSe2 single crystals* *Project supported by the National Key Research and Development Program of China (Grant Nos. 2016YFA0302400, 2016YFA0300602, and 2017YFA0302903), the National Natural Science Foundation of China (Grant No. 11227903), the Beijing Municipal Science and Technology Commission, China (Grant Nos. Z181100004218007 and Z191100007219011), the National Basic Research Program of China

Interface can be a fertile ground for exotic quantum states, including topological superconductivity, Majorana mode, fractal quantum Hall effect, unconventional superconductivity, Mott insulator, etc. Here we grow single-unit-cell (1UC) FeTe film on NbSe2 single crystal by molecular beam epitaxy (MBE) and investigate the film in-situ with a home-made cryogenic scanning tunneling microscopy (STM) and non-contact atomic force microscopy (AFM) combined system. We find different stripe-like superlattice modulations on grown FeTe film with different misorientation angles with respect to NbSe2 substrate. We show that these stripe-like superlattice modulations can be understood as moiré pattern forming between FeTe film and NbSe2 substrate. Our results indicate that the interface between FeTe and NbSe2 is atomically sharp. By STM–AFM combined measurement, we suggest that the moiré superlattice modulations have an electronic origin when the misorientation angle is relatively small (≤ 3°) and have structural relaxation when the misorientation angle is relatively large (≥ 10°).

Azobindungsbildung auf Metalloberflächen

AbstractDie Bildung von Azoverbindungen durch Redoxkreuzkupplung von Nitroarenen und Arylaminen, welche in Lösungsmittelchemie herausfordernd ist, wird durch Oberflächenchemie ermöglicht. Die Reaktionsprodukte werden mit einem kryogenen Rastertunnelmikroskop (STM) und per Röntgenphotoelektronenspektroskopie (XPS) analysiert. Durch die Verwendung gut konzipierter Vorläufer, welche eine Amino‐ und eine Nitrofunktion enthalten, werden Azopolymere durch hocheffiziente Nitro‐Amino‐Kreuzkupplung auf der Oberfläche hergestellt. Experimente mit anderen Substraten und Oberflächenorientierungen zeigen, dass die Metalloberfläche einen signifikanten Einfluss auf die Reaktionseffizienz hat. Zudem wurde herausgefunden, dass die Reaktion partiell oxidierter/reduzierter Vorläuferverbindungen in Dimerisierungsreaktionen ebenfalls stattfindet, was Licht auf den Mechanismus wirft, welcher durch DFT‐Berechnungen weiter untersucht wurde.

Azo bond formation on metal surfaces.

The formation of azo compounds via redox cross‐coupling of nitroarenes and arylamines, challenging in solution phase chemistry, is achieved by on‐surface chemistry. Reaction products are analyzed with a cryogenic scanning tunneling microscope (STM) and X‐ray photoelectron spectroscopy (XPS). By using well‐designed precursors containing both an amino and a nitro functionality, azo polymers are prepared on surface via highly efficient nitro‐amino cross‐coupling. Experiments conducted on other substrates and surface orientations reveal that the metal surface has a significant effect on the reaction efficiency. The reaction was further found to proceed from partially oxidized/reduced precursors in dimerization reactions, shedding light on the mechanism that was studied by DFT calculations.

The Raman Spectrum of a Single Molecule on an Electrochemically Etched Silver Tip.

We recorded the Raman spectrum of a single azobenzene thiol molecule upon picking it up from an atomically flat gold surface, using an electrochemically etched silver tip, in an ultrahigh vacuum cryogenic scanning tunneling microscope. While suppressed at the junction, the stationary spectrum appeared once the molecule was transferred to the tip, with line intensities that increased by a factor of ∼5 as the tip was retracted from 1 nm to 161 nm. The effect, and the enhanced tensorial Raman spectrum was reproduced using an explicit treatment of the electromagnetic fields to identify a cis-azobenzene thiol molecule, adsorbed on a nanometric asperity removed from the tip apex, lying in the plane normal to the tip z-axis, with enhanced incident and radiative local fields polarized in the same plane. Tips decorated with asperities break the rules and give unique insights on Raman driven by cavity modes of a plasmonic junction.

Unidirectional growth of graphene nano-islands from carbon cluster seeds on Ge(1 1 0)

The anisotropic twofold symmetry of Ge(110) makes it a unique substrate for the growth of single-crystalline graphene. However, the underlying mechanism during the initial stage of growth of graphene on Ge(110) surface is not well understood. Here, we use in-situ cryogenic scanning tunneling microscopy (STM) and spectroscopy (STS), to study the initial growth properties of graphene synthesized on Ge(110) surface with ethylene precursor gases. The STM results reveal that the unidirectional growth of the graphene nanoribbons (GNRs) initiates from carbon cluster seeds on terraces during the early stage of the growth. The orientations of the GNRs show the same directions which are nearly parallel to the 1¯10direction of the Ge(110) surface. This orientation is the same as that of the wafer-scale graphene grown on Ge(110). Subsequent growth, transformed the GNRs to graphene nanoislands (GNIs), which eventually coalesced to form single crystalline monolayer graphene. STS measurements demonstrated that the GNRs have small bandgaps induced by the confinement effect of graphene. This study provides an in-depth understanding of the growth mechanism of graphene on Ge(110) surface in various synthesis conditions.

Stoichiometry and defect superstructures in epitaxial FeSe films on SrTiO3

Cryogenic scanning tunneling microscopy is employed to investigate the stoichiometry and defects of epitaxial FeSe thin films on ${\mathrm{SrTiO}}_{3}$(001) substrates under various postgrowth annealing conditions. Low-temperature annealing with an excess supply of Se leads to the formation of Fe vacancies and superstructures, accompanied by a superconductivity (metal)-to-insulator transition in FeSe films. By contrast, high-temperature annealing could eliminate the Fe vacancies and superstructures, and thus recover the high-temperature superconducting phase of monolayer FeSe films. We also observe multilayer FeSe during low-temperature annealing, which is revealed to link with Fe vacancy formation and adatom migration. Our results document the very special roles of film stoichiometry and help unravel several controversies in the properties of monolayer FeSe films.

Tunable Thiolate Coordination Networks on Metal Surfaces

AbstractThiolate coordination networks (TCNs) were synthesized on metal surfaces using benzenehexathiol (BHT) and analyzed by cryogenic scanning tunneling microscopy (STM), X‐ray photoelectron spectroscopy (XPS) as well as density functional theory. Upon adsorption, the deprotonation of the thiol groups occurred on the metal surface with the formation of metal‐sulfur coordination bonds. Increasing the surface temperature triggered the complete dehydrogenation of BHT and promoted the formation of TCNs. On Ag(111), the TCN of [Ag3(C6S6)]n was achieved and showed good thermal stability. On Cu(111), two TCNs ([Cu6(C6S6)]n and [Cu8(C6S6)]n,) were identified. Interestingly, the construction of the two TCNs on Cu(111) can be precisely controlled by adjusting the temperature of the surface during deposition and thermal annealing. Our results reveal the significant influence of the metal surface on the formation of coordination networks.