Design and performance of an ultrahigh vacuum spectroscopic-imaging scanning tunneling microscope with a hybrid vibration isolation system.

A spectroscopic imaging-scanning tunneling microscope (SI-STM) allows for the atomic scale visualization of the surface electronic and magnetic structure of novel quantum materials with a high energy resolution. To achieve the optimal performance, a low vibration facility is required. Here, we describe the design and performance of an ultrahigh vacuum STM system supported by a hybrid vibration isolation system that consists of a pneumatic passive and a piezoelectric active vibration isolation stage. We present the detailed vibrational noise analysis of the hybrid vibration isolation system, which shows that the vibration level can be suppressed below 10-8 m/sec/√Hz for most frequencies up to 100 Hz. Combined with a rigid STM design, vibrational noise can be successfully removed from the tunneling current. We demonstrate the performance of our STM system by taking high resolution spectroscopic maps and topographic images on several quantum materials. Our results establish a new strategy to achieve an effective vibration isolation system for high-resolution STM and other scanning probe microscopies to investigate the nanoscale quantum phenomena.

Ultrafast carrier dynamics and layer-dependent carrier recombination rate in InSe.

InSe layered semiconductors with high mobility have advantages over transition-metal dichalcogenides in certain device applications. Understanding the dynamics of carriers, especially around the major bandgaps, is not only of fundamental interest but also important for improving the performance of devices. We investigated ultrafast carrier dynamics in exfoliated InSe near the bandgap and found that the presence of photocarriers led to shrinkage in the optical bandgap. In addition, we observed that the carrier recombination rate increased when the thickness of the InSe nanoflakes was reduced and the process was dominated by surface recombination. For the same flakes, the recombination rate became lower after the freshly exfoliated InSe was exposed to air and oxidized. Using a free carrier diffusion model, layer-dependent surface recombination velocities were obtained. Our investigation reveals that the surface condition and the thickness of few-layer InSe play important roles in carrier lifetimes.

Dirac Nodal Line in Hourglass Semimetal Nb3SiTe6.

Glide-mirror symmetry in nonsymmorphic crystals can foster the emergence of novel hourglass nodal loop states. Here, we present spectroscopic signatures from angle-resolved photoemission of a predicted topological hourglass semimetal phase in Nb3SiTe6. Linear band crossings are observed at the zone boundary of Nb3SiTe6, which could be the origin of the nontrivial Berry phase and are consistent with a predicted glide quantum spin Hall effect; such linear band crossings connect to form a nodal loop. Furthermore, the saddle-like Fermi surface of Nb3SiTe6 observed in our results helps unveil linear band crossings that could be missed. In situ alkali-metal doping of Nb3SiTe6 also facilitated the observation of other band crossings and parabolic bands at the zone center correlated with accidental nodal loop states. Overall, our results complete the system's band structure, help explain prior Hall measurements, and suggest the existence of a nodal loop at the zone center of Nb3SiTe6.

Atomically-resolved interlayer charge ordering and its interplay with superconductivity in YBa2Cu3O6.81.

High-temperature superconductive (SC) cuprates exhibit not only a SC phase, but also competing orders, suppressing superconductivity. Charge order (CO) has been recognized as an important competing order, but its microscopic spatial interplay with SC phase as well as the interlayer coupling in CO and SC phases remain elusive, despite being essential for understanding the physical mechanisms of competing orders and hence superconductivity. Here we report the achievement of direct real-space imaging with atomic-scale resolution of cryogenically cleaved YBa2Cu3O6.81 using cross-sectional scanning tunneling microscopy/spectroscopy. CO nanodomains are found embedded in the SC phase with a proximity-like boundary region characterized by mutual suppression of CO and superconductivity. Furthermore, SC coherence as well as CO occur on both CuO chain and plane layers, revealing carrier transport and density of states mixing between layers. The CO antiphase correlation along the c direction suggests a dominance of Coulomb repulsion over Josephson tunneling between adjacent layers.

Observing quantum trapping on MoS2 through the lifetimes of resonant electrons: revealing the Pauli exclusion principle.

We demonstrate that the linewidth of the field emission resonance (FER) observed on the surface of MoS2 using scanning tunneling microscopy can vary by up to one order of magnitude with an increasing electric field. This phenomenon originates from quantum trapping, in which the electron relaxed from a resonant electron in the FER is momentarily trapped in a potential well on the MoS2 surface due to its wave nature. Because the relaxed electron and the resonant electron have the same spin, through the action of the Pauli exclusion principle, the lifetimes of the resonant electrons can be substantially prolonged when the relaxed electrons engage in resonance trapping. The linewidth of the FER is thus considerably reduced to as narrow as 12 meV. The coexistence of the resonant electron and the relaxed electron requires the emission of two electrons, which can occur through the exchange interaction.

Thermoelectric Figure-of-Merit of Fully Dense Single-Crystalline SnSe.

Single-crystalline SnSe has attracted much attention because of its record high figure-of-merit ZT ≈ 2.6; however, this high ZT has been associated with the low mass density of samples which leaves the intrinsic ZT of fully dense pristine SnSe in question. To this end, we prepared high-quality fully dense SnSe single crystals and performed detailed structural, electrical, and thermal transport measurements over a wide temperature range along the major crystallographic directions. Our single crystals were fully dense and of high purity as confirmed via high statistics 119Sn Mössbauer spectroscopy that revealed <0.35 at. % Sn(IV) in pristine SnSe. The temperature-dependent heat capacity (C p) provided evidence for the displacive second-order phase transition from Pnma to Cmcm phase at T c ≈ 800 K and a small but finite Sommerfeld coefficient γ0 which implied the presence of a finite Fermi surface. Interestingly, despite its strongly temperature-dependent band gap inferred from density functional theory calculations, SnSe behaves like a low-carrier-concentration multiband metal below 600 K, above which it exhibits a semiconducting behavior. Notably, our high-quality single-crystalline SnSe exhibits a thermoelectric figure-of-merit ZT ∼1.0, ∼0.8, and ∼0.25 at 850 K along the b, c, and a directions, respectively.

Tunable Moiré Superlattice of Artificially Twisted Monolayers.

Twisting between two stacked monolayers modulates periodic potentials and forms the Moiré electronic superlattices, which offers an additional degree of freedom to alter material property. Considerable unique observations, including unconventional superconductivity, coupled spin-valley states, and quantized interlayer excitons are correlated to the electronic superlattices but further study requires reliable routes to study the Moiré in real space. Scanning tunneling microscopy (STM) is ideal to precisely probe the Moiré superlattice and correlate coupled parameters among local electronic structures, strains, defects, and band alignment at atomic scale. Here, a clean route is developed to construct twisted lattices using synthesized monolayers for fundamental studies. Diverse Moiré superlattices are predicted and successfully observed with STM at room temperature. Electrical tuning of the Moiré superlattice is achieved with stacked TMD on graphite.

The design and the performance of an ultrahigh vacuum 3He fridge-based scanning tunneling microscope with a double deck sample stage for in-situ tip treatment.

Scanning tunneling microscope (STM) is a powerful tool for studying the structural and electronic properties of materials at the atomic scale. The combination of low temperature and high magnetic field for STM and related spectroscopy techniques allows us to investigate the novel physical properties of materials at these extreme conditions with high energy resolution. Here, we present the construction and the performance of an ultrahigh vacuum 3He fridge-based STM system with a 7 Tesla superconducting magnet. It features a double deck sample stage on the STM head so we can clean the tip by field emission or prepare a spin-polarized tip in situ without removing the sample from the STM. It is also capable of in situ sample and tip exchange and preparation. The energy resolution of scanning tunneling spectroscopy at T = 310 mK is determined to be 400 mK by measuring the superconducting gap with a niobium tip on a gold surface. We demonstrate the performance of this STM system by imaging the bicollinear magnetic order of Fe1+xTe at T = 5 K.

Geometric quenching of orbital pair breaking in a single crystalline superconducting nanomesh network.

In a superconductor Cooper pairs condense into a single state and in so doing support dissipation free charge flow and perfect diamagnetism. In a magnetic field the minimum kinetic energy of the Cooper pairs increases, producing an orbital pair breaking effect. We show that it is possible to significantly quench the orbital pair breaking effect for both parallel and perpendicular magnetic fields in a thin film superconductor with lateral nanostructure on a length scale smaller than the magnetic length. By growing an ultra-thin (2 nm thick) single crystalline Pb nanowire network, we establish nm scale lateral structure without introducing weak links. Our network suppresses orbital pair breaking for both perpendicular and in-plane fields with a negligible reduction in zero-field resistive critical temperatures. Our study opens a frontier in nanoscale superconductivity by providing a strategy for maintaining pairing in strong field environments in all directions with important technological implications.

Atomically Resolved Electronic States and Correlated Magnetic Order at Termination Engineered Complex Oxide Heterointerfaces.

We map electronic states, band gaps, and interface-bound charges at termination-engineered BiFeO3/La0.7Sr0.3MnO3 interfaces using atomically resolved cross-sectional scanning tunneling microscopy. We identify a delicate interplay of different correlated physical effects and relate these to the ferroelectric and magnetic interface properties tuned by engineering the atomic layer stacking sequence at the interfaces. This study highlights the importance of a direct atomically resolved access to electronic interface states for understanding the intriguing interface properties in complex oxides.

Xenon gas field ion source from a single-atom tip.

Focused ion beam (FIB) systems have become powerful diagnostic and modification tools for nanoscience and nanotechnology. Gas field ion sources (GFISs) built from atomic-size emitters offer the highest brightness among all ion sources and thus can improve the spatial resolution of FIB systems. Here we show that the Ir/W(111) single-atom tip (SAT) can emit high-brightness Xe+ ion beams with a high current stability. The ion emission current versus extraction voltage was analyzed from 150 K up to 309 K. The optimal emitter temperature for maximum Xe+ ion emission was ∼150 K and the reduced brightness at the Xe gas pressure of 1 × 10-4 torr is two to three orders of magnitude higher than that of a Ga liquid metal ion source, and four to five orders of magnitude higher than that of a Xe inductively coupled plasma ion source. Most surprisingly, the SAT emitter remained stable even when operated at 309 K. Even though the ion current decreased with increasing temperature, the current at room temperature (RT) could still reach over 1 pA when the gas pressure was higher than 1 × 10-3 torr, indicating the feasibility of RT-Xe-GFIS for application to FIB systems. The operation temperature of Xe-SAT-GFIS is considerably higher than the cryogenic temperature required for the helium ion microscope (HIM), which offers great technical advantages because only simple or no cooling schemes can be adopted. Thus, Xe-GFIS-FIB would be easy to implement and may become a powerful tool for nanoscale milling and secondary ion mass spectroscopy.

Spatially Resolved Imaging on Photocarrier Generations and Band Alignments at Perovskite/PbI2 Heterointerfaces of Perovskite Solar Cells by Light-Modulated Scanning Tunneling Microscopy.

The presence of the PbI2 passivation layers at perovskite crystal grains has been found to considerably affect the charge carrier transport behaviors and device performance of perovskite solar cells. This work demonstrates the application of a novel light-modulated scanning tunneling microscopy (LM-STM) technique to reveal the interfacial electronic structures at the heterointerfaces between CH3NH3PbI3 perovskite crystals and PbI2 passivation layers of individual perovskite grains under light illumination. Most importantly, this technique enabled the first observation of spatially resolved mapping images of photoinduced interfacial band bending of valence bands and conduction bands and the photogenerated electron and hole carriers at the heterointerfaces of perovskite crystal grains. By systematically exploring the interfacial electronic structures of individual perovskite grains, enhanced charge separation and reduced back recombination were observed when an optimal design of interfacial PbI2 passivation layers consisting of a thickness less than 20 nm at perovskite crystal grains was applied.

Sharpness-induced energy shifts of quantum well states in Pb islands on Cu(111).

We elucidate that the tip sharpness in scanning tunneling microscopy (STM) can be characterized through the number of field-emission (FE) resonances. A higher number of FE resonances indicates higher sharpness. We observe empty quantum well (QW) states in Pb islands on Cu(111) under different tip sharpness levels. We found that QW states observed by sharper tips always had lower energies, revealing negative energy shifts. This sharpness-induced energy shift originates from an inhomogeneous electric field in the STM gap. An increase in sharpness increases the electric field inhomogeneity, that is, enhances the electric field near the tip apex, but weakens the electric field near the sample. As a result, higher sharpness can increase the electronic phase in vacuum, causing the lowering of QW state energies. Moreover, the behaviors of negative energy shift as a function of state energy are entirely different for Pb islands with a thickness of two and nine atomic layers. This thickness-dependent behavior results from the electrostatic force in the STM gap decreasing with increasing tip sharpness. The variation of the phase contributed from the expansion deformation induced by the electrostatic force in a nine-layer Pb island is significantly greater, sufficient to effectively negate the increase of electronic phase in vacuum.

A Metal-Insulator Transition of the Buried MnO2 Monolayer in Complex Oxide Heterostructure.

A novel artificially created MnO2 monolayer system is demonstrated in atomically controlled epitaxial perovskite heterostructures. With careful design of different electrostatic boundary conditions, a magnetic transition as well as a metal-insulator transition of the MnO2 monolayer is unveiled, providing a fundamental understanding of dimensionality-confined strongly correlated electron systems and a direction to design new electronic devices.

Dopant Diffusion and Activation in Silicon Nanowires Fabricated by ex Situ Doping: A Correlative Study via Atom-Probe Tomography and Scanning Tunneling Spectroscopy.

Dopants play a critical role in modulating the electric properties of semiconducting materials, ranging from bulk to nanoscale semiconductors, nanowires, and quantum dots. The application of traditional doping methods developed for bulk materials involves additional considerations for nanoscale semiconductors because of the influence of surfaces and stochastic fluctuations, which may become significant at the nanometer-scale level. Monolayer doping is an ex situ doping method that permits the post growth doping of nanowires. Herein, using atom-probe tomography (APT) with subnanometer spatial resolution and atomic-ppm detection limit, we study the distributions of boron and phosphorus in ex situ doped silicon nanowires with accurate control. A highly phosphorus doped outer region and a uniformly boron doped interior are observed, which are not predicted by criteria based on bulk silicon. These phenomena are explained by fast interfacial diffusion of phosphorus and enhanced bulk diffusion of boron, respectively. The APT results are compared with scanning tunneling spectroscopy data, which yields information concerning the electrically active dopants. Overall, comparing the information obtained by the two methods permits us to evaluate the diffusivities of each different dopant type at the nanowire oxide, interface, and core regions. The combined data sets permit us to evaluate the electrical activation and compensation of the dopants in different regions of the nanowires and understand the details that lead to the sharp p-i-n junctions formed across the nanowire for the ex situ doping process.

Field enhancement factors and self-focus functions manifesting in field emission resonances in scanning tunneling microscopy.

Field emission (FE) resonance (or Gundlach oscillation) in scanning tunneling microscopy (STM) is a phenomenon in which the FE electrons emitted from the microscope tip couple into the quantized standing-wave states within the STM tunneling gap. Although the occurrence of FE resonance peaks can be semi-quantitatively described using the triangular potential well model, it cannot explain the experimental observation that the number of resonance peaks may change under the same emission current. This study demonstrates that the aforementioned variation can be adequately explained by introducing a field enhancement factor that is related to the local electric field at the tip apex. The peak number of FE resonances increases with the field enhancement factor. The peak intensity of the FE resonance on the reconstructed Au(111) surface varies in the face-center cubic, hexagonal-close-packed, and ridge regions, thus providing the contrast in the mapping through FE resonances. The mapping contrast is demonstrated to be nearly independent of the tip-sample distance, implying that the FE electron beam is not divergent because of a self-focus function intrinsically involved in the STM configuration.

Superconducting topological surface states in the noncentrosymmetric bulk superconductor PbTaSe2.

The search for topological superconductors (TSCs) is one of the most urgent contemporary problems in condensed matter systems. TSCs are characterized by a full superconducting gap in the bulk and topologically protected gapless surface (or edge) states. Within each vortex core of TSCs, there exists the zero-energy Majorana bound states, which are predicted to exhibit non-Abelian statistics and to form the basis of the fault-tolerant quantum computation. To date, no stoichiometric bulk material exhibits the required topological surface states (TSSs) at the Fermi level (EF) combined with fully gapped bulk superconductivity. We report atomic-scale visualization of the TSSs of the noncentrosymmetric fully gapped superconductor PbTaSe2. Using quasi-particle scattering interference imaging, we find two TSSs with a Dirac point at E ≅ 1.0 eV, of which the inner TSS and the partial outer TSS cross EF, on the Pb-terminated surface of this fully gapped superconductor. This discovery reveals PbTaSe2 as a promising candidate for TSC.

Effect of focused ion beam deposition induced contamination on the transport properties of nano devices.

Focused ion beam (FIB) deposition produces unwanted particle contamination beyond the deposition point. This is due to the FIB having a Gaussian distribution. This work investigates the spatial extent of this contamination and its influence on the electrical properties of nano-electronic devices. A correlation study is performed on carbon-nanotube (CNT) devices manufactured using FIB deposition. The devices are observed using transmission electron microscopy (TEM) and these images are correlated with device electrical characteristics. To discover how far Pt-nanoparticle contamination occurs along a CNT after FIB electrical contact deposition careful TEM inspections are performed. The results show FIB deposition efficiently improves electrical contact; however, the practice is accompanied by serious particle contamination near deposition points. These contaminants include metal particles and amorphous elements originating from precursor gases and residual water molecules in the vacuum chamber. Pt-contamination extends for approximately 2 µm from the point of FIB contact deposition. These contaminants cause current fluctuations and alter the transport characteristics of devices. It is recommended that nano-device fabrication occurs at a distance greater than 2 µm from the FIB deposition of an electrical contact.

Scanning tunneling microscopy/spectroscopy of picene thin films formed on Ag(111).

Using ultrahigh-vacuum low-temperature scanning tunneling microscopy and spectroscopy combined with first principles density functional theory calculations, we have investigated structural and electronic properties of pristine and potassium (K)-deposited picene thin films formed in situ on a Ag(111) substrate. At low coverages, the molecules are uniformly distributed with the long axis aligned along the [112̄] direction of the substrate. At higher coverages, ordered structures composed of monolayer molecules are observed, one of which is a monolayer with tilted and flat-lying molecules resembling a (11̄0) plane of the bulk crystalline picene. Between the molecules and the substrate, the van der Waals interaction is dominant with negligible hybridization between their electronic states; a conclusion that contrasts with the chemisorption exhibited by pentacene molecules on the same substrate. We also observed a monolayer picene thin film in which all molecules were standing to form an intermolecular π stacking. Two-dimensional delocalized electronic states are found on the K-deposited π stacking structure.

Parallel p-n junctions across nanowires by one-step ex situ doping.

The bottom-up synthesis of nanoscale building blocks is a versatile approach for the formation of a vast array of materials with controlled structures and compositions. This approach is one of the main driving forces for the immense progress in materials science and nanotechnology witnessed over the past few decades. Despite the overwhelming advances in the bottom-up synthesis of nanoscale building blocks and the fine control of accessible compositions and structures, certain aspects are still lacking. In particular, the transformation of symmetric nanostructures to asymmetric nanostructures by highly controlled processes while preserving the modified structural orientation still poses a significant challenge. We present a one-step ex situ doping process for the transformation of undoped silicon nanowires (i-Si NWs) to p-type/n-type (p-n) parallel p-n junction configuration across NWs. The vertical p-n junctions were measured by scanning tunneling microscopy (STM) in concert with scanning tunneling spectroscopy (STS), termed STM/S, to obtain the spatial electronic properties of the junction formed across the NWs. Additionally, the parallel p-n junction configuration was characterized by off-axis electron holography in a transmission electron microscope to provide an independent verification of junction formation. The doping process was simulated to elucidate the doping mechanisms involved in the one-step p-i-n junction formation.