Sharp Metal Tip Research Articles

Double Tips for In-Plane Polarized Near-Field Microscopy and Spectroscopy.

Near-field optical microscopy and spectroscopy provide high-resolution imaging below the diffraction limit, crucial in physics, chemistry, and biology for studying molecules, nanoparticles, and viruses. These techniques use a sharp metallic tip of an atomic force microscope (AFM) to enhance incoming and scattered light by excited near-fields at the tip apex, leading to high sensitivity and a spatial resolution of a few nanometers. However, this restricts the near-field orientation to out-of-plane polarization, limiting optical polarization choices. We introduce double tips that offer in-plane polarization for enhanced imaging and spectroscopy. These double tips provide superior enhancement over single tips, although with a slightly lower spatial resolution (∼30 nm). They enable advanced studies of nanotubes, graphene defects, and transition metal dichalcogenides, benefiting from polarization control. The double tips allow varied polarization in tip-enhanced Raman scattering and selective excitation of transverse-electric and -magnetic polaritons, expanding the range of nanoscale samples that can be studied.

Tracing attosecond electron emission from a nanometric metal tip.

Solids exposed to intense electric fields release electrons through tunnelling. This fundamental quantum process lies at the heart of various applications, ranging from high brightness electron sources in d.c. operation1,2 to petahertz vacuum electronics in laser-driven operation3-8. In the latter process, the electron wavepacket undergoes semiclassical dynamics9,10 in the strong oscillating laser field, similar to strong-field and attosecond physics in the gas phase11,12. There, the subcycle electron dynamics has been determined with a stunning precision of tens of attoseconds13-15, but at solids the quantum dynamics including the emission time window has so far not been measured. Here we show that two-colour modulation spectroscopy of backscattering electrons16 uncovers the suboptical-cycle strong-field emission dynamics from nanostructures, with attosecond precision. In our experiment, photoelectron spectra of electrons emitted from a sharp metallic tip are measured as function of the relative phase between the two colours. Projecting the solution of the time-dependent Schrödinger equation onto classical trajectories relates phase-dependent signatures in the spectra to the emission dynamics and yields an emission duration of 710 ± 30 attoseconds by matching the quantum model to the experiment. Our results open the door to the quantitative timing and precise active control of strong-field photoemission from solid state and other systems and have direct ramifications for diverse fields such as ultrafast electron sources17, quantum degeneracy studies and sub-Poissonian electron beams18-21, nanoplasmonics22 and petahertz electronics23.

Driving a Third Generation Molecular Motor with Electrons Across a Surface.

Excitation of single molecules with electrons tunneling between a sharp metallic tip of a scanning tunneling microscope and a metal surface is one way to study and control dynamics of molecules on surfaces. Electron tunneling induced dynamics may lead to hopping, rotation, molecular switching, or chemical reactions. Molecular motors that convert rotation of subgroups into lateral movement on a surface can in principle also be driven by tunneling electrons. For such surface-bound motor molecules the efficiency of motor action with respect to electron dose is still not known. Here, the response of a molecular motor containing two rotor units in the form of overcrowded alkene groups to inelastic electron tunneling has been examined on a Cu(111) surface in ultrahigh vacuum at 5 K. Upon vibrational excitation, switching between different molecular conformations is observed, including conversion of enantiomeric states of chiral conformations. Tunneling at energies in the range of electronic excitations causes activation of motor action and movement across the surface. The expected unidirectional rotation of the two rotor units causes forward movements but with a low degree of translational directionality.

(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

Strong Parametric Coupling between Two Ultracoherent Membrane Modes.

We demonstrate parametric coupling between two modes of a silicon nitride membrane. We achieve the coupling by applying an oscillating voltage to a sharp metal tip that approaches the membrane surface to within a few 100nm. When the voltage oscillation frequency is equal to the mode frequency difference, the modes exchange energy periodically and faster than their free energy decay rate. This flexible method can potentially be useful for rapid state control and transfer between modes, and is an important step toward parametric spin sensing experiments with membrane resonators.

Field emission microscope for a single fullerene molecule

Applying strong direct current (DC) electric fields on the apex of a sharp metallic tip, electrons can be radially emitted from the apex to vacuum. Subsequently, they magnify the nanoscopic information on the apex, which serves as a field emission microscope (FEM). When depositing molecules on such a tip, peculiar electron emission patterns such as clover leaves appear. These phenomena were first observed seventy years ago. However, the source of these emission patterns has not yet been identified owing to the limited experimental information about molecular configurations on a tip. Here, we used fullerene molecules and characterized the molecule-covered tip by an FEM. In addition to the experiments, simulations were performed to obtain optimized molecular configurations on a tip. Both results indicate that the molecules, the source of the peculiar emission patterns, appear on a molecule layer formed on the tip under strong DC electric fields. Furthermore, the simulations revealed that these molecules are mostly isolated single molecules forming single-molecule-terminated protrusions. Upon the excellent agreements in both results, we concluded that each emission pattern originates from a single molecule. Our work should pave the way to revive old-fashioned electron microscopy as a powerful tool for investigating a single molecule.

(Invited) Scanning Gate Imaging of Charge Transport in Graphene Nanodevices

Quantum transport in nanodevices is usually probed thanks to measurements of the electrical resistance or conductance, which lack the spatial resolution necessary to probe local-scale electron behaviour. Here, we will discuss how to get real-space local information on peculiar quantum transport phenomena inside graphene constrictions. The results were obtained using low temperature scanning gate microscopy (SGM), which consists in mapping the electrical conductance of a device as an electrically-biased sharp metallic tip scans in its vicinity [1].If the tip-induced perturbation is relatively small, SGM is an imaging technique giving access to the local density of states inside mesoscopic devices [2]. Here, we will focus on the regime of large tip-induced perturbation. This regime is particularly interesting in the case of graphene: depending on tip voltage and tip-sample distance, one can tune the shape, size, and smoothness of the moving scattering region associated with the tip, and eventually create a moving circular pn-junction within the device. We use this moving pn-junction to probe peculiar aspects of relativistic charge carrier dynamics within graphene devices: Klein tunnelling and current focusing and defocusing [3], Fabry-Pérot interferometry [4], signatures of whispering gallery modes [5] and tunneling between counterpropagating quantum Hall edge states [6]. This work unlocks new possibilities in the field of electron optics in graphene.[1] M.A. Eriksson et al., Appl. Phys. Lett. 69, 671 (1996); M. Topinka et al., Science 289, 671 (2000).[2] F. Martins et al., Phys. Rev. Lett. 99, 136807 (2007) ; M. Pala et al., Phys. Rev. B 77, 125310 (2008).[3] B. Brun et al., Phys. Rev. B 100, 041401 (2019).[4] B. Brun et al., 2D Materials, 7, 025037 (2020).[5] B. Brun et al., submitted.[6] N. Moreau et al., submitted.

Understanding the Role of Different Substrate Geometries for Achieving Optimum Tip-Enhanced Raman Scattering Sensitivity.

Tip-enhanced Raman spectroscopy (TERS) has experienced tremendous progress over the last two decades. Despite detecting single molecules and achieving sub-nanometer spatial resolution, attaining high TERS sensitivity is still a challenging task due to low reproducibility of tip fabrication, especially regarding very sharp tip apices. Here, we present an approach for achieving strong TERS sensitivity via a systematic study of the near-field enhancement properties in the so-called gap-mode TERS configurations using the combination of finite element method (FEM) simulations and TERS experiments. In the simulation study, a gold tip apex is fixed at 80 nm of diameter, and the substrate consists of 20 nm high gold nanodiscs with diameter varying from 5 nm to 120 nm placed on a flat extended gold substrate. The local electric field distributions are computed in the spectral range from 500 nm to 800 nm with the tip placed both at the center and the edge of the gold nanostructure. The model is then compared with the typical gap-mode TERS configuration, in which a tip of varying diameter from 2 nm to 160 nm is placed in the proximity of a gold thin film. Our simulations show that the tip-nanodisc combined system provides much improved TERS sensitivity compared to the conventional gap-mode TERS configuration. We find that for the same tip diameter, the spatial resolution achieved in the tip-nanodisc model is much better than that observed in the conventional gap-mode TERS, which requires a very sharp metal tip to achieve the same spatial resolution on an extended metal substrate. Finally, TERS experiments are conducted on gold nanodisc arrays using home-built gold tips to validate our simulation results. Our simulations provide a guide for designing and realization of both high-spatial resolution and strong TERS intensity in future TERS experiments.

Label-Free Near-Infrared Plasmonic Sensing Technique for DNA Detection at Ultralow Concentrations.

Biomolecular detection at a low concentration is usually the most important criterion for biological measurement and early stage disease diagnosis. In this paper, a highly sensitive nanoplasmonic biosensing approach is demonstrated by achieving near‐infrared plasmonic excitation on a continuous gold‐coated nanotriangular array. Near‐infrared incident light at a small incident angle excites surface plasmon resonance with much higher spectral sensitivity compared with traditional configuration, due to its greater interactive volume and the stronger electric field intensity. By introducing sharp nanotriangular metallic tips, intense localization of plasmonic near‐fields is realized to enhance the molecular perception ability on sensing surface. This approach with an enhanced sensitivity (42103.8 nm per RIU) and a high figure of merit (367.812) achieves a direct assay of ssDNA at nanomolar level, which is a further step in label‐free ultrasensitive sensing technique. Considerable improvement is recorded in the detection limit of ssDNA as 1.2 × 10−18 m based on the coupling effect between nanotriangles and gold nanoparticles. This work combines high bulk‐ and surface‐sensitivities, providing a simple way toward label‐free ultralow‐concentration biomolecular detection.

Tip-Based Plasmonic Nanofocusing: Vector Field Engineering and Background Elimination

Nearly thirty years ago, Specht et al. proposed a new optical near-field microscope based on the interaction of surface plasmons and a sharp metal tip. Since then, the tip-based plasmonic nanofocusing has been widely studied. When the tip-based plasmonic nanofocusing integrated with scanning probe microscopy, it not only forms highly localized enhanced electric field to boost the spectral signal but also simultaneously provides morphological information. These amazing properties provide a new detection method to understand the nano-world, including spatial structures of chemicals and physical, electronic and catalytic properties of substance. Upon growing demand for background-free nanofocusing, more and more attention is being drawn to developing new technologies for it. Hitherto, owing to the salient properties, tip-based background-free nanofocusing have tremendous advanced applications such as ultrafast optics, nonlinear optics, and even electron emission. This article reviews the historical developments from fundamentals to the techniques for tip-based plasmonic nanofocusing and then to their advanced applications.

(Invited) Scanning Gate Imaging of Charge Transport in Graphene Nanodevices

Quantum transport in nanodevices is usually probed thanks to measurements of the electrical resistance or conductance, which lack the spatial resolution necessary to probe local-scale electron behavior. Here, we will discuss how to get real-space local information on peculiar quantum transport phenomena inside graphene constrictions. The results were obtained using low temperature scanning gate microscopy (SGM), which consists in mapping the electrical conductance of a device as an electrically-biased sharp metallic tip scans in its vicinity [1].If the tip-induced perturbation is relatively small, SGM is an imaging technique giving access to the local density of states inside mesoscopic devices [2]. Here, we will focus on the regime of large tip-induced perturbation. This regime is particularly interesting in the case of graphene: depending on tip voltage and tip-sample distance, one can tune the shape, size, and smoothness of the moving scattering region associated with the tip, and eventually create a moving circular pn-junction within the device. We use this moving pn-junction to probe peculiar aspects of relativistic charge carrier dynamics within graphene devices: Klein tunnelling and current focusing and defocusing [3], Fabry-Pérot interferometry [4] and signatures of whispering gallery modes. This work unlocks new possibilities in the field of electron optics in graphene.[1] M.A. Eriksson et al., Appl. Phys. Lett. 69, 671 (1996); M. Topinka et al., Science 289, 671 (2000).[2] F. Martins et al., Phys. Rev. Lett. 99, 136807 (2007) ; M. Pala et al., Phys. Rev. B 77, 125310 (2008).[3] B. Brun et al., Phys. Rev. B 100, 041401 (2019).[4] B. Brun et al., arXiv:1911.12031.

Quantifying Nanoscale Electromagnetic Fields in Near-Field Microscopy by Fourier Demodulation Analysis

Confining light to sharp metal tips has become a versatile technique to study optical and electronic properties far below the diffraction limit. Particularly near-field microscopy in the mid-infrared spectral range has found a variety of applications in probing nanostructures and their dynamics. Yet, the ongoing quest for ultimately high spatial resolution down to the single-nanometer regime and quantitative three-dimensional nano-tomography depends vitally on a precise knowledge of the spatial distribution of the near fields emerging from the probe. Here, we perform finite element simulations of a tip with realistic geometry oscillating above a dielectric sample. By introducing a novel Fourier demodulation analysis of the electric field at each point in space, we reliably quantify the distribution of the near fields above and within the sample. Besides inferring the lateral field extension, which can be smaller than the tip radius of curvature, we also quantify the probing volume within the sample. Finally, we visualize the scattering process into the far field at a given demodulation order, for the first time, and shed light onto the nanoscale distribution of the near fields and its evolution as the tip-sample distance is varied. Our work represents a crucial step in understanding and tailoring the spatial distribution of evanescent fields in optical nanoscopy.

Infrared rectification based on electron field emission in nanoantennas for thermal energy harvesting

ABSTRACT A rectification concept based on field electron emission in a nanoantenna is proposed. The device consists of three parts, i.e., an aspherical micro-lens, a nanoantenna, and an electron collector electrode with proper geometry design to ensure rectified field electron emission. The incident radiation is enhanced in two steps, firstly by micro-lens focusing onto the nanoantenna, and secondly through excitation of the near field in the gap of the nanoantenna to reach a level required for field electron emission from a sharp metallic tip. Furthermore, we show that single nanoantenna cells can be arranged into an array using a bus-bar configuration where the currents of each cell are added up to increase the harvested power. The performance of the nanoantenna in a single cell and in the array is studied by full-wave simulations. Finally, the total efficiency of the proposed device is calculated to demonstrate its superiority over the MIM devices.

Nanoscale spectroscopic origins of photoinduced tip–sample force in the midinfrared

When light illuminates the junction formed between a sharp metal tip and a sample, different mechanisms can contribute to the measured photoinduced force simultaneously. Of particular interest are the instantaneous force between the induced dipoles in the tip and in the sample, and the force related to thermal heating of the junction. A key difference between these 2 force mechanisms is their spectral behavior. The magnitude of the thermal response follows a dissipative (absorptive) Lorentzian line shape, which measures the heat exchange between light and matter, while the induced dipole response exhibits a dispersive spectrum and relates to the real part of the material polarizability. Because the 2 interactions are sometimes comparable in magnitude, the origin of the chemical selectivity in nanoscale spectroscopic imaging through force detection is often unclear. Here, we demonstrate theoretically and experimentally how the light illumination gives rise to the 2 kinds of photoinduced forces at the tip-sample junction in the midinfrared. We comprehensively address the origin of the spectroscopic forces by discussing cases where the 2 spectrally dependent forces are entwined. The analysis presented here provides a clear and quantitative interpretation of nanoscale chemical measurements of heterogeneous materials and sheds light on the nature of light-matter coupling in optomechanical force-based spectronanoscopy.

Preparing a Celadonite Electron Source and Estimating Its Brightness.

The electron celadonite source described here performs well in a low-energy electron point-source projection microscope in long-range imaging. It presents major advantages compared to sharp metal tips. Its robustness affords a lifetime of months and it can be used under relatively high pressure. The celadonite crystal is deposited at the apex of a carbon fiber, maintained itself in a coaxial structure ensuring a spherical beam shape and easy mechanical positioning to align the source, the object and the electron-optical system axis. There is a single crystal deposition via generation of celadonite-containing water droplets with a micropipette. Scanning electron microscopy observation can be performed to verify the deposition. However, this adds steps and therefore increases the risk of damaging the source. Thus, after preparation, the source is usually inserted directly under vacuum in the projection microscope. A first high voltage supply provides the kick-off needed to start the electron emission. The field emission process involved is then measured: it has already been observed for dozens of electron sources prepared in this way. The brightness is under-estimated through an over-estimation of source size, intensity at one energy and cone angle measured in a projection system.

Exciton-Plasmon Energy Exchange Drives the Transition to a Strong Coupling Regime.

We present a model for exciton-plasmon coupling based on an energy exchange mechanism between quantum emitters (QE) and localized surface plasmons in metal-dielectric structures. Plasmonic correlations between QEs give rise to a collective state exchanging its energy cooperatively with a resonant plasmon mode. By defining carefully the plasmon mode volume for a QE ensemble, we obtain a relation between QE-plasmon coupling and a cooperative energy transfer rate that is expressed in terms of local fields. For a single QE near a sharp metal tip, we find analytically the enhancement factor for QE-plasmon coupling relative to QE coupling to a cavity mode. For QEs distributed in an extended region enclosing a plasmonic structure, we find that the ensemble QE-plasmon coupling saturates to a universal value independent of system size and shape, consistent with the experiment.

Perspective: Nanoscopy of charge kinetics via terahertz fluctuation

A novel scanning microscope, which visualizes kinetics of charges by mapping ultrahigh frequency current fluctuation (15–30 THz), is described. This microscope, called the scanning noise microscope, scatters a fluctuating electromagnetic evanescent field on the sample surface with a sharp metal tip and detects the scattered field with an ultrahighly sensitive THz detector in a THz confocal microscope. This article describes the basic concept of the microscope, highlights the uniqueness and the general importance of the method, and demonstrates the powerfulness of the method by exemplifying experimental results made on (i) nanostructured metal layers in thermal equilibrium, (ii) narrow metal wires under non-uniform Joule heating, and (iii) operating GaAs nano-devices with non-local hot-electron energy dissipation in a highly non-equilibrium condition.

Structure reactivity relationships during N2O hydrogenation over Au-Ag alloys: A study by field emission techniques

To make available atomic oxygen at the surface of a catalyst is the key step for oxidation reactions on Au-based catalysts. In this context, Au-Ag alloys catalysts exhibit promising properties for selective oxidation reactions of alcohols: low temperature activity and high selectivity. The presence of O(ads) and its effects on the catalytic reactivity is studied via the N2O dissociative adsorption and subsequent hydrogenation. Field emission techniques are particularly suited to study this reaction: Field Ion Microscopy (FIM) and Field Emission Microscopy (FEM) enable to image the extremity of sharp metallic tips, the size and morphology of which are close to those of one single catalytic particle.The reaction dynamics is studied in the 300–320 K temperature range and at a pressure of 3.5 × 10−3 Pa. The main results are a strong structure/reactivity relationship during N2O + H2 reaction over Au-8.8 at.%Ag model catalysts. Comparison of high-resolution FIM images of the clean sample and FEM images during reaction shows a sensitivity of the reaction to the local structure of the facets, independently of the used partial pressures of both N2O and H2. This suggests a localised dissociative adsorption step for N2O and H2 with the formation of a reactive interface around the {210} facets.

Multiband plasmonic nanoantenna structure for infrared energy harvesting based on electron field emission rectification

AbstractIn this article, a multiband, planar, direct energy rectification, and dual polarized infrared plasmonic nanoantenna is presented and numerically simulated using finite element method (FEM). Broadband characteristics are highly suitable for energy harvesting applications. The proposed nanoantenna structure comprises cross bowtie aluminum structures deposited on the silicon dioxide (SiO2) substrate. In the proposed device, incoming thermal electromagnetic energy is first enhanced by micro‐lenses through focusing the thermal energy onto the nanoantenna. Then, further enhancement is achieved using several nanoantennas, each with different resonance length, to achieve enough electrical field for electron field emission from sharp metallic tips in their gaps. Each nanoantenna resonates in the proper wavelength, electrical field is enhanced in the gap, and finally, a total current is generated from electron field emissions. The calculated current, based on Fowler‐Nordheim theory, matches well with the simulation results. The total current of the proposed nanostructure is superposition of the produced current of each nanoantenna. To our best knowledge, this is the first report on a multiband nanostructure for energy harvesting. As a typical implementation, a structure is designed for energy absorption in the mid infrared wavelengths, 1‐4 µm.

Tracing the phase of focused broadband laser pulses

Precise knowledge of the behaviour of the phase of light in a focused beam is fundamental to understanding and controlling laser-driven processes. More than a hundred years ago an axial phase anomaly for focused monochromatic light beams was discovered and is now commonly known as the Gouy phase. Recent theoretical work has brought into question the validity of applying this monochromatic phase formulation to the broadband pulses becoming ubiquitous today. Based on electron back-scattering at sharp nanometre-scale metal tips, a method is available to measure light fields with sub-wavelength spatial resolution and sub-optical cycle time resolution. Here we report such a direct, three-dimensional measurement of the spatial dependence of the optical phase of a focused, 4-fs, near-infrared laser pulse. The observed optical phase deviates substantially from the monochromatic Gouy phase - exhibiting a much more complex spatial dependence, both along the propagation axis and in the radial direction. In our measurements, these significant deviations are the rule and not the exception for focused, broadband laser pulses. Therefore, we expect wide ramifications for all broadband laser-matter interactions, such as in high-harmonic and attosecond pulse generation, femtochemistry, ophthalmological optical coherence tomography and light-wave electronics.