Resonant Field Emission Research Articles

Tip-induced local Fermi level alignment: A Stark shift in vacuum level in scanning tunneling microscope configurations

Electric fields in the junction of a scanning tunneling microscope (STM) are generally considered to have a negligible impact on the vacuum level (VL) of materials. We employed field emission resonance (FER) in the STM, combined with the triangular potential model, to measure the VL of the Ag(100) surface under varying electric currents. Unexpectedly, our results reveal that the VL exhibits a linear positive energy shift with increasing electric field strength. We suggest that this Stark shift in the VL arises from local Fermi level alignment induced by the STM tip. Additionally, we examined the VL of Ag islands grown on Cu(111) and Au(111) surfaces under different currents. Despite the Ag island having a lower work function than the Cu(111) and Au(111) surfaces, the energy shift in the VL with respect to the electric field on the Ag island is almost identical to that on the substrate under the same tip structure. This suggests that the Stark shift of the VL is insensitive to the work function. These findings are crucial for utilizing FER to measure local work function variations on surfaces, as the measured value is not influenced by the STM tip structure or the tunneling current, both of which can alter the electric field.

Probing the graphene/substrate interaction by electron tunneling decay

The electronic properties of graphene can be modified by the local interaction with a selected metal substrate. To probe this effect, Scanning Tunneling Microscopy is widely employed, particularly by means of local measurement via lock-in amplifier of the differential conductance and of the field emission resonance. In this article we propose an alternative, reliable method of probing the graphene/substrate interaction that is readily available to any STM apparatus. By testing the tunneling current as function of the tip/sample distance on nanostructured graphene on Ni(100) and Ir (100), we demonstrate that I(z) spectroscopy can be quantitatively compared with Density Functional Theory calculations and can be used to assess the nature of the interaction between graphene and substrate. This method can expand the capabilities of standard STM systems to study graphene/substrate complexes, complementing standard topographic probing with spectroscopic information.

A van der Waals Heterostructure with an Electronically Textured Moiré Pattern: PtSe2/PtTe2

The interlayer interaction in Pt-dichalcogenides strongly affects their electronic structures. The modulations of the interlayer atom-coordination in vertical heterostructures based on these materials are expected to laterally modify these interlayer interactions and thus provide an opportunity to texture the electronic structure. To determine the effects of local variation of the interlayer atom coordination on the electronic structure of PtSe2, van der Waals heterostructures of PtSe2 and PtTe2 have been synthesized by molecular beam epitaxy. The heterostructure forms a coincidence lattice with 13 unit cells of PtSe2 matching 12 unit cells of PtTe2, forming a moiré superstructure. The interaction with PtTe2 reduces the band gap of PtSe2 monolayers from 1.8 eV to 0.5 eV. While the band gap is uniform across the moiré unit cell, scanning tunneling spectroscopy and dI/dV mapping identify gap states that are localized within certain regions of the moiré unit cell. Deep states associated with chalcogen pz-orbitals at binding energies of ∼ -2 eV also exhibit lateral variation within the moiré unit cell, indicative of varying interlayer chalcogen interactions. Density functional theory calculations indicate that local variations in atom coordination in the moiré unit cell cause variations in the charge transfer from PtTe2 to PtSe2, thus affecting the value of the interface dipole. Experimentally this is confirmed by measuring the local work function by field emission resonance spectroscopy, which reveals a large work function modulation of ∼0.5 eV within the moiré structure. These results show that the local coordination variation of the chalcogen atoms in the PtSe2/PtTe2 van der Waals heterostructure induces a nanoscale electronic structure texture in PtSe2.

Normalization procedure for obtaining the local density of states from high-bias scanning tunneling spectroscopy

Differential conductance spectroscopy performed in the high bias regime---in which the applied voltage exceeds the sample work function---is a suboptimal measure of the local density of states due to the effects of the changing tunnel barrier. Additionally, the large applied voltage oftentimes makes constant-height measurement experimentally impractical, lending constant-current spectroscopy an advantageous edge; but the differential conductance in that case is even further removed from the local density of states due to the changing tip height. Here, we present a normalization scheme for extracting the local density of states from high bias scanning tunneling spectroscopy, obtained in either constant-current or constant-height mode. We extend this model to account for the effects of the in-plane momentum of the probed states to the overall current. We demonstrate the validity of the proposed scheme by applying it to laterally confined field-emission resonances, which appear as peak-shaped spectroscopic features with a well-defined in-plane momentum.

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.

Field-Emission Resonances in Thin Metallic Films: Nonexponential Decrease of the Tunneling Current as a Function of the Sample-to-Tip Distance

Field-Emission Resonances in Thin Metallic Films: Nonexponential Decrease of the Tunneling Current as a Function of the Sample-to-Tip Distance

Characterization of apex structures of scanning tunneling microscope tips with field emission resonance energies

The apex structure of a scanning tunneling microscope (STM) tip consists of a base with radius of tens of nanometers and protrusion with atomic-scale sharpness. We characterized the tip base radius and sharpness on the basis of field emission resonance (FER) energies. We derived two quantities from the first- through sixth-order FER energies, which were related to tip sharpness and base radius. The base radius can remain unchanged while the sharpness varied, and the tips can have identical sharpness but different base radii. The base radius can significantly affect the peak intensities of FER, which corresponds to the mean lifetime of FER electrons, on a Ag(100) surface but not on those of FER on a Ag(111) surface. This difference results from the surface dipole layer and quantum trapping effect (QTE) on the Ag(100) surface which are greater than those on the Ag(111) surface.

Confined Vacuum Resonances as Artificial Atoms with Tunable Lifetime.

Atomically engineered artificial lattices are a useful tool for simulating complex quantum phenomena, but have so far been limited to the study of Hamiltonians where electron–electron interactions do not play a role. However, it is precisely the regime in which these interactions do matter where computational times lend simulations a critical advantage over numerical methods. Here, we propose a platform for constructing artificial matter that relies on the confinement of field-emission resonances, a class of vacuum-localized discretized electronic states. We use atom manipulation of surface vacancies in a chlorine-terminated Cu(100) surface to reveal square patches of the underlying metal, thereby creating atomically precise potential wells that host particle-in-a-box modes. By adjusting the dimensions of the confining potential, we can access states with different quantum numbers, making these patches attractive candidates as quantum dots or artificial atoms. We demonstrate that the lifetime of electrons in these engineered states can be extended and tuned through modification of the confining potential, either via atomic assembly or by changing the tip–sample distance. We also demonstrate control over a finite range of state filling, a parameter which plays a key role in the evolution of quantum many-body states. We model the transport through the localized state to disentangle and quantify the lifetime-limiting processes, illustrating the critical dependence of the electron lifetime on the properties of the underlying bulk band structure. The interplay with the bulk bands gives rise to negative differential resistance, leading to possible applications in engineering custom atomic-scale resonant tunnelling diodes, which exhibit similar current–voltage characteristics.

Probing tip-induced attractive deformation of graphite surfaces through wave function dissipation in field emission resonance

We studied wave function dissipation (WFD) in field emission resonance (FER) by performing scanning tunneling microscopy on the highly oriented pyrolytic graphite (HOPG) and Ag(111) surfaces under two conditions: (1) the same current and FER number; (2) the same tip structure but different currents. Under the first condition, we observed that the decay rate corresponding to the WFD exhibited a larger variation on the HOPG surface than it did on the Ag(111) surface. Under the second condition, the decay rate was nearly independent of the FER electric field for the Ag(111) surface; by contrast, it was linearly proportional to the FER electric field for the HOPG surface. These remarkable differences can be attributed to the factors that the tip-induced attractive deformation caused by the electrostatic force was considerably more prominent on the HOPG surface than on the Ag(111) surface and that the deformed HOPG top layer had a unique electronic structure similar to that of single-layer graphene.

Impact of band structure on wave function dissipation in field emission resonance

We demonstrated on Ag(111) and Ag(100) surfaces that the reciprocal of the field emission resonance (FER) linewidth, which is proportional to the mean lifetime of resonant electrons in FER, may vary with the electric field. The variation on Ag(111) was nearly smooth, whereas that on Ag(100) was sporadic and fluctuated remarkably. This drastic difference can be explained through their dissimilar projected bulk band structures and the ensemble interpretation of quantum mechanics, according to which all resonant electrons are governed by a single wave function (WF). Ag(100) has an energy gap above its vacuum level, whereas Ag(111) does not. Consequently, the dissipation rate of the WF, which is relevant to the FER linewidth, on Ag(111) was almost stable, whereas that on Ag(100) fluctuated. The fluctuation originated from the quantum trapping effect and surface dipole layer (SDL) on Ag(100) surface. Through FER linewidth, we also demonstrated that SDLs of Cu(100) and Ag(100) are different.

Termination-dependent electronic structure and atomic-scale screening behavior of the Cu2O(111) surface

By combining differential conductance (dI/dV) spectroscopy with a scanning tunneling microscope and hybrid density functional theory simulations we explore the electronic characteristics of the (1 × 1) and (√3 × √3)R30° terminations of the Cu2O(111) surface close to thermodynamic equilibrium. Although frequently observed experimentally, the composition and atomic structure of these two terminations remain controversial. Our results show that their measured electronic signatures, such as the conduction band onset deduced from dI/dV measurements, the bias-dependent appearance of surface topographic features, as well as the work function retrieved from field emission resonances unambiguously confirm their recent assignment to a (1 × 1) Cu-deficient (CuD) and a (√3 × √3)R30° nano-pyramidal reconstruction. Moreover, we demonstrate that due to a different localization of the screening charges at these Cu-deficient terminations, their electronic characteristics qualitatively differ from those of the stoichiometric (1 × 1) and O-deficient (√3 × √3) terminations often assumed in the literature. As a consequence, aside from the topographic differences recently pointed out, also their electronic characteristics may contribute to a radical change in the common perception of the Cu2O(111) surface reactivity.

Copper oxide phases probed via plasmonic light emission in the STM

Luminescence spectroscopy with a scanning tunnelling microscope (STM) is employed to differentiate bulk-type Cu2O from a Cu3O2 surface oxide at the nanometre scale. Although plasmonic modes in the tunnelling gap are responsible for the emission response in both cases, the luminescence cross-section shows a characteristic dependence on bias voltage for the two oxide phases. On the Cu3O2 surface oxide, the emission yield peaks at the 1st field emission resonance of the STM junction, when particularly high inelastic tunnelling rates are realized between tip and sample. On Cu2O(111) patches, on the other hand, direct and defect-mediated electron recombination from the oxide conduction to the valence band is responsible for plasmon excitations in the STM cavity. Given the different excitation mechanisms, Cu2O and Cu3O2 oxide regions become distinguishable in bias-dependent STM luminescence maps with nanometre precision. We expect this optical contrast scheme to be applicable whenever blends of dielectric materials with different band gaps coexist on the surface.

Borophene synthesis beyond the single-atomic-layer limit.

Synthetic two-dimensional (2D) materials have no bulk counterparts and typically exist as single atomic layers due to substrate-stabilized growth. Multilayer formation, although broadly sought for structure and property tuning, has not yet been achieved in the case of synthetic 2D boron: that is, borophene1,2. Here, we experimentally demonstrate the synthesis of an atomically well-defined borophene polymorph beyond the single-atomic-layer (SL) limit. The structure of this bilayer (BL) borophene is consistent with two covalently bonded α-phase layers (termed BL-α borophene) as evidenced from bond-resolved scanning tunnelling microscopy, non-contact atomic force microscopy and density functional theory calculations. While the electronic density of states near the Fermi level of BL-α borophene is similar to SL borophene polymorphs, field-emission resonance spectroscopy reveals distinct interfacial charge transfer doping and a heightened local work function exceeding 5 eV. The extension of borophene polymorphs beyond the SL limit significantly expands the phase space for boron-based nanomaterials.

Local stiffness and work function variations of hexagonal boron nitride on Cu(111).

Combined scanning tunnelling and atomic force microscopy using a qPlus sensor enables the measurement of electronic and mechanic properties of two-dimensional materials at the nanoscale. In this work, we study hexagonal boron nitride (h-BN), an atomically thin 2D layer, that is van der Waals-coupled to a Cu(111) surface. The system is of interest as a decoupling layer for functional 2D heterostructures due to the preservation of the h-BN bandgap and as a template for atomic and molecular adsorbates owing to its local electronic trapping potential due to the in-plane electric field. We obtain work function (Φ) variations on the h-BN/Cu(111) superstructure of the order of 100 meV using two independent methods, namely the shift of field emission resonances and the contact potential difference measured by Kelvin probe force microscopy. Using 3D force profiles of the same area we determine the relative stiffness of the Moiré region allowing us to analyse both electronic and mechanical properties of the 2D layer simultaneously. We obtain a sheet stiffness of 9.4 ± 0.9 N·m−1, which is one order of magnitude higher than the one obtained for h-BN/Rh(111). Using constant force maps we are able to derive height profiles of h-BN/Cu(111) showing that the system has a corrugation of 0.6 ± 0.2 Å, which helps to demystify the discussion around the flatness of the h-BN/Cu(111) substrate.

Nanoscale Probing of Image-Potential States and Electron Transfer Doping in Borophene Polymorphs.

Because synthetic 2D materials are generally stabilized by interfacial coupling to growth substrates, direct probing of interfacial phenomena is critical for understanding their nanoscale structure and properties. Using field-emission resonance spectroscopy with an ultrahigh vacuum scanning tunneling microscope, we reveal Stark-shifted image-potential states of the v1/6 and v1/5 borophene polymorphs on Ag(111) with long lifetimes, suggesting high borophene lattice and interface quality. These image-potential states allow the local work function and interfacial charge transfer of borophene to be probed at the nanoscale and test the widely employed self-doping model of borophene. Supported by apparent barrier height measurements and density functional theory calculations, electron transfer doping occurs for both borophene phases from the Ag(111) substrate. In contradiction with the self-doping model, a higher electron transfer doping level occurs for denser v1/6 borophene compared to v1/5 borophene, thus revealing the importance of substrate effects on borophene electron transfer.

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.

Plasmon-Assisted Resonant Electron Tunneling in a Scanning Tunneling Microscope Junction.

We report plasmon-assisted resonant electron tunneling from a Ag or Au tip to field emission resonances (FERs) of a Ag(111) surface induced by cw laser excitation of a scanning tunneling microscope (STM) junction at visible wavelengths. As a hallmark of the plasmon-assisted resonant tunneling, we observe a downshift of the first peak in the FER spectra by a fixed amount equal to the incident photon energy. STM-induced luminescence measurement for the Ag and Au tip reveals the clear correlation between the laser-induced change in the FER spectra and the plasmonic properties of the junction. Our results clarify a novel resonant electron transfer mechanism in a plasmonic nanocavity.

Characterization of external potential for field emission resonances and its applications on nanometer-scale measurements

The form of the external potential (FEP) for generating field emission resonance (FER) in a scanning tunneling microscopy (STM) junction is usually assumed to be triangular. We demonstrate that this assumption can be examined using a plot that can characterize FEP. The plot is FER energies versus the corresponding distances between the tip and sample. Through this energy–distance relationship, we discover that the FEP is nearly triangular for a blunt STM tip. However, the assumption of a triangular potential form is invalid for a sharp tip. The disparity becomes more severe as the tip is sharper. We demonstrate that the energy–distance plot can be exploited to determine the barrier width in field emission and estimate the effective sharpness of an STM tip. Because FERs were observed on Pb islands grown on the Cu(111) surface in this study, determination of the tip sharpness enabled the derivation of the subtle expansion deformation of Pb islands due to electrostatic force in the STM junction.

Generalized Mechanism of Field Emission from Nanostructured Semiconductor Film Cathodes

Considering the effect of both the buffer layer and substrate, a series of ultrathin multilayered structure cathodes (UTMC) is constructed to simulate the field emission (FE) process of nanostructured semiconductor film cathodes (NSFCs). We find a generalized FE mechanism of the NSFCs, in which there are three distinct FE modes with the change of the applied field. Our results clearly show significant differences of FE between conventional emitters and nanofilm emitters, which the non-Fowler-Nordheim characteristics and the resonant FE will be inevitable for NSFCs. Moreover, the controllable FE can be realized by fine-tuning the quantum structure of NSFCs. The generalized mechanism of NSFCs presented here may be particularly useful for design high-speed and high-frequency vacuum nano-electronic devices.

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.