Single-atom Tip Research Articles

Reliable preparation and regeneration of well-defined single-atom tips through laser annealing.

Single-atom tips (SATs) have crucial scientific and technological applications, such as in scanning probe microscopy and charged particle beam technology. We reported a reliable method of preparing and regenerating noble metal-covered W(111) SATs through laser annealing at approximately 1000 K under ultrahigh vacuum. The field emission patterns obtained during laser heating revealed the self-assembly process of a pyramidal tip. The SATs can be regenerated through laser annealing tens of times with little change in sharpness, indicating a long lifetime. Various pyramidal SATs can be generated and regenerated using visible-light, near-infrared, mode-locked, and continuous-wave lasers at different polarizations relative to the tip axis. The generation of well-defined pyramidal SATs through laser annealing can facilitate various applications of SATs.

Directly anchoring non-noble metal single atoms on 1T-TMDs with tip structure for efficient hydrogen evolution

Owing to tip effect can introduce localized enhanced electric field and reduce interfacial energy barrier, design of atomic tip structure in single-atom catalysts (SACs) may be a fascinating strategy to further improve its electrocatalytic activity. However, conventional synthesis methods, such as defect-trapping or substitution, only lead to the formation of planar geometry of SACs without tip atoms. Good conductive 1T-TMDs with electrocatalytically active basal plane can provide platform to directly stabilize single atoms (SAs) on the top sites of its surface to form atomic tip structure. Herein, a universal Laser-molecular beam epitaxy (L-MBE) method for precisely controlling non-noble metal SAs directly immobilizing on the Cr top site of 1T-CrS2 metallic basal plane is developed. In case of Mo, the Mo SAs@1T-CrS2 with single-atom tip structure can exhibit enhanced electric field surrounding Mo atoms and an almost zero hydrogen adsorption free energy, resulting in superior HER performance together with high stability. This work provides a general way to design varieties of SACs in widely catalytic application.

Field Assisted Reactive Gas Etching of Multiple Tips Observed using FIM

A simple and cost effective method to fabricate multiple tungsten (W) single atom tips (SATs) from both poly and single crystalline wires is reported. Two or four tips attached to a holder are electrochemically etched together in NaOH solution followed by a controlled field assisted reactive gas etching in vacuum using nitrogen as an etching gas and helium as an imaging gas. A Common high voltage is applied simultaneously to all nanotips to shape the apexes towards single atoms. Single atom tips were achieved for both W(111) and W(110) while trimer tips were also achieved for W(111). This observation can lead to an important step towards realizing simplified etching processes of multiple tips which in turn can help to simultaneously fabricate numerous tips leading to mass fabrication and characterization.

Effective radius of adatoms/single atom of polycrystalline W nanotip in gas field ion source

A gas field ion source (GFIS) has several advantages such as high current density, low energy spread, and high brightness. In this study, Helium gas was used in a GFIS, generated using the field ionization and field evaporation processes. The (110) oriented three adatoms tip (TAT) and single atom tip (SAT) were prepared with its ion emission stability 9.8% and 10.1% by the nitrogen field-assisted etching, respectively. The TAT and SAT were reproduced throughout the field evaporation and nitrogen field-assisted etching along the same crystal axis with its brightness 2.6 × 107 A/(m2 sr) and 1.6 × 108 A/(m2 sr), respectively. The field emission electron beam effective radii for three adatoms and single atom were calculated to be 2.90 Å and 1.47 Å, respectively, by Fowler-Nordheim plot, in which the single atom size was especially shown to be quite in good consistency with an atomic radius of tungsten.

Characteristics Comparison of Neon, Argon, and Krypton Ion Emissions from Gas Field Ionization Sources with a Single-Atom Tip.

A scanning ion beam instrument equipped with a gas field ionization source (GFIS) has been commercialized, but only helium and neon are currently available as GFISs. In this study, the characteristics of neon, argon, and krypton ion emissions from a single-atom tip are compared, specifically for faster fabrication by milling of a silicon sample. Although the boiling point of argon is about 87 K, our experiments on characterizing argon ion emission can be carried out at temperatures of about 50 K at an argon gas pressure lower than 0.1 Pa. Argon exhibits ion current characteristics, as a function of tip voltage, between those of neon and krypton. The value obtained by multiplying the ion emission current by the sputtering yield is suitable for a figure of merit (FOM) for faster fabrication. The FOM for argon is the highest among the three ion species. This value must be extensively evaluated from the viewpoint of practical nano-fabrication application. The instabilities of neon, argon, and krypton ion currents (3σ) become as low as 8% in 1 h, which is sufficient for fabrication applications. We conclude that an argon or krypton GFIS ion beam instrument will be a useful tool for nano-fabrication.

Sexiphenyl on Cu(100): nc-AFM tip functionalization and identification

The contrast obtained in scanning tunneling microscopy (STM) and atomic force microscopy (AFM) images is determined by the tip termination and symmetry. Functionalizing the tip with a single metal atom, CO molecule or organic species has been shown to provide high spatial resolution and insights into tip-surface interactions. A topic where this concept is utilized is the adsorption of organic molecules at surfaces. With this work we aim to contribute to the growing database of organic molecules that allow assignment by intra-molecular imaging. We investigated the organic molecule para-sexiphenyl (C36H26, 6P) on Cu(100) using low-temperature STM and non-contact AFM with intra-molecular resolution. In the sub-monolayer regime we find a planar and flat adsorption with the 6P molecules rotated 10° off the 〈010〉 directions. In this configuration, four of six phenyl rings occupy almost equivalent sites on the surface. The 6P molecules are further investigated with CO-functionalized tips, in comparison to a single-atom metal and 6P-terminated tip. We also show that the procedure of using adsorbed CO to characterize tips introduced by Hofmann et al., Phys. Rev. B 112 (2014) 066101 is useful when the tip is terminated with an organic molecule.

Coherent properties of a tunable low-energy electron-matter-wave source

A general challenge in various quantum experiments and applications is to develop suitable sources for coherent particles. In particular, recent progress in microscopy, interferometry, metrology, decoherence measurements and chip based applications rely on intensive, tunable, coherent sources for free low energy electron matter waves. In most cases, the electrons get field emitted from a metal nanotip where its radius and geometry towards a counter electrode determines the field distribution and the emission voltage. A higher emission is often connected to faster electrons with smaller de Broglie wavelengths, requiring larger pattern magnification after matter wave diffraction or interferometry. This can be prevented with a well-known setup consisting of two counter electrodes that allow independent setting of the beam intensity and velocity. However, it needs to be tested if the coherent properties of such a source are preserved after the acceleration and deceleration of the electrons. Here, we study the coherence of the beam in a biprism interferometer with a single atom tip electron field emitter if the particle velocity and wavelength varies after emission. With a Wien filter measurement and a contrast correlation analysis we demonstrate that the intensity of the source at a certain particle wavelength can be enhanced up to a factor of 33 without changing the transverse and longitudinal coherence of the electron beam. In addition, the energy width of the single atom tip emitter was measured to be 377 meV, corresponding to a longitudinal coherence length of 82 nm. The design has potential applications in interferometry, microscopy and sensor technology

Selective production of hydrogen ion species at atomically designed nanotips

Hydrogen scanning ion microscopy systems rely on nanotip gas field ion sources to generate the hydrogen ion beam. The exact structure of the nanotip and the applied electric field are shown to be important. It is demonstrated that hydrogen ion beams are found to occur as mixtures of H+, H2+ and H3+ depending on the electric field strength and the nanotip structure. Various nanotips were prepared, including single atom tips (SATs), trimers and other nano-structured tips to compare the contents of hydrogen ion beams. It was found that single atom tips produce primarily H2+ at low operating voltages, but as the voltage is increased, H3+ dominates. For the trimer case, H2+ becomes a significant species and equals the H3+ current but H3+ can be isolated at higher voltages. For the hexamer tip structure, H2+ almost completely dominates with little H3+ being produced. H+ is only observed in small quantities for all tip structures until a high voltage regime, where apex atom resolution is not observed. Comparisons W SATs and Ir SATs showed similar H3+/H2+ product ratios indicating the nanotip structure plays a key role in the catalytic formation of H3+. Temperature affects are also discussed and operating parameters for single species ion beams are discussed.

Ultrabright and monochromatic nanowire electron sources

Abstract

Comparison of Characteristics of Neon, Argon, and Krypton Ion Emissions from Gas Field Ionization Source with Single Atom Tip

Comparison of Characteristics of Neon, Argon, and Krypton Ion Emissions from Gas Field Ionization Source with Single Atom Tip

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.

Characteristics of krypton ion emission from a gas field ionization source with a single atom tip

A scanning ion beam instrument equipped with a gas field ionization source (GFIS) has been commercialized, but only helium and neon are currently available as GFISs. The characteristics of krypton ion emission from a single atom tip (SAT) have not been reported yet. In this study, the characteristics of krypton ion emission were investigated by field ion microscopy. At 65 K, the krypton ion emission current reached approximately 40 pA, which is 1 order of magnitude higher than that at 130 K. As the krypton gas pressure was increased, the krypton ion current increased. At a pressure of 0.3 Pa, the emission current was anticipated to reach 200 pA, which may be high enough for nanofabrication. The variation of the krypton ion current was as low as 5% in one hour. We concluded that a krypton ion beam instrument equipped with a GFIS will be a powerful tool for nanofabrication.

Influence of atomic tip structure on the intensity of inelastic tunneling spectroscopy data analyzed by combined scanning tunneling spectroscopy, force microscopy, and density functional theory

Achieving a high intensity in inelastic scanning tunneling spectroscopy (IETS) is important for precise measurements. The intensity of the IETS signal can vary up to a factor three for various tips without an apparent reason accessible by scanning tunneling microscopy (STM) alone. Here, we show that combining STM and IETS with atomic force microscopy enables carbon monoxide front atom identification, revealing that high IETS intensities for CO/Cu(111) are obtained for single atom tips, while the intensity drops sharply for multi-atom tips. Adsorbing the CO molecule on a Cu adatom [CO/Cu/Cu(111)] such that it is elevated over the substrate strongly diminishes the tip dependence of IETS intensity, showing that an elevated position channels most of the tunneling current through the CO molecule even for multi-atom tips, while a large fraction of the tunneling current bypasses the CO molecule in the case of CO/Cu(111).

Iridium single atom tips fabricated by field assisted reactive gas etching

We present a simple, reliable method to fabricate Ir single atom tips (SATs) from polycrystalline wire. An electrochemical etch in CaCl2 solution is followed by a field assisted reactive gas etch in vacuum at room temperature using oxygen as an etching gas and neon as an imaging gas. Once formed, SATs are cooled to liquid nitrogen temperatures and their underlying structure is examined through evaporation of the apex atoms. Furthermore, a method is developed to repair Ir SATs at liquid nitrogen temperatures when apex atoms evaporate. This method may be used to fabricate Ir SAT ion sources.

Characterization and modeling of nanotips fabricated in the field ion microscope

AbstractNanotips are considered significant elements in some of nanotechnology instruments. They are used in scanning probe microscopes and electron microscopes to characterize materials at the nano and atomic scales. Therefore, the size and profile of the nanotip determines the performance of these microscopes. The advancement of nanotip fabrication techniques has enabled the fabrication of ultra-sharp tips and even single-atom tips. However, the characterization of nanotips with an apex of a few nanometers is still premature, while the conventional characterization methods of the tip size, such as the ring counting method, have shown some limitation at this nano scale. In this paper, we review the various nanotip fabrication methods with a focus on the most recent one, which is called the local electron bombardment method. We demonstrate an approach for estimating the nanotip radius with good approximation using ball crystal models. We also model the overall nanotip profile using finite element simulation tools based on the hyperboloidal geometry. The modeling and radius estimation approach is applied on tips fabricated by the local electron bombardment method, which will be explained in detail as well.

Effective beam separation schemes for the measurement of the electric Aharonov–Bohm effect in an ion interferometer

We propose an experiment for the first proof of the type I electric Aharonov–Bohm effect in an ion interferometer for hydrogen. The performances of three different beam separation schemes are simulated and compared. The coherent ion beam is generated by a single atom tip (SAT) source and separated by either two biprisms with a quadrupole lens, two biprisms with an einzel-lens or three biprisms. The beam path separation is necessary to introduce two metal tubes that can be pulsed with different electric potentials. The high time resolution of a delay line detector allows to work with a continuous ion beam and circumvents the pulsed beam operation as originally suggested by Aharonov and Bohm. We demonstrate that the higher mass and therefore lower velocity of ions compared to electrons combined with the high expected SAT ion emission puts the direct proof of this quantum effect for the first time into reach of current technical possibilities. Thereby a high detection rate of coherent ions is crucial to avoid long integration times that allow the influence of dephasing noise from the environment. We can determine the period of the expected matter wave interference pattern and the signal on the detector by determining the superposition angle of the coherent partial beams. Our simulations were tested with an electron interferometer setup and agree with the experimental results. We determine the separation scheme with three biprisms to be most efficient and predict a total signal acquisition time of only 80s to measure a phase shift from 0 to 2π due to the electric Aharonov–Bohm effect.

Fabrication of Mo pyramidal-shape single atom tips covered by a noble metal

• Provide another option for a material to produce single atom tips. • Selecting an oxide that is easier to remove from the surface of the metal is important in the manufacture of single-atom tips. • The single atom tips will have a self-assembled formation after annealing the Mo tips covered by noble metal. • There are two types of pyramidal structures formed on Mo (1 1 1) facets. The effect of annealing temperature on the faceting phenomena has been studied for pure molybdenum (Mo) and Mo tips covered with palladium (Pd), platinum (Pt), rhodium (Rh), or iridium (Ir) by field ion microscopy (FIM). For these Mo samples, three {2 1 1} facets were found to expand to {1 1 1} facets and form pyramidal structures after annealing at the temperature of 1100–1300 K. The pyramidal single atom tips (SATs) were formed on Pd-, Pt- and Rh-covered Mo tips. Two types of pyramidal structure, stacked by either 1, 3, 10 or 1, 6, 15 atoms for the top three layers were found. However, no SATs were found on pure Mo and Ir-covered tips. This indicates that noble metal adsorption, which can increase the difference of surface-free-energy anisotropy, indeed benefits the formation of SATs on Mo systems. Additionally, an SAT cannot be obtained for the Ir-covered Mo systems, because Ir is easily alloyed with Mo.

Biprism electron interferometry with a single atom tip source

Experiments with electron or ion matter waves require a coherent, monochromatic and long-term stable source with high brightness. These requirements are best fulfilled by single atom tip (SAT) field emitters. The performance of an iridium covered W(111) SAT is demonstrated and analyzed for electrons in a biprism interferometer. Furthermore we characterize the emission of the SAT in a separate field electron and field ion microscope and compare it with other emitter types. A new method is presented to fabricate the electrostatic charged biprism wire that separates and combines the matter wave. In contrast to other biprism interferometers the source and the biprism size are well defined within a few nanometers. The setup has direct applications in ion interferometry and Aharonov-Bohm physics.

Robustness of tungsten single atom tips to thermal treatment and air exposure

Experiments aimed at assessing the robustness of nitrogen-etched, single-atom tips (SATs) prepared using W(111) single crystal wire were performed. Our experiments showed that single-atoms tips sustain minimal damage when exposed to atmospheric conditions and can be readily and quickly nitrogen-etched to single-atom tips thereafter. The SATs can be annealed at temperatures up to 1100°C with minimal shape changes. Moreover, annealing temperatures in excess of 1200°C resulted in an apex faceting which may prove important in further single-atom tip creation. Procedures for warming of the SATs from operating temperatures of 80K were also evaluated to determine conditions that limit tip contamination. These results show that SATS could be fabricated in a dedicated vacuum system and subsequently transferred to other instruments where they would undergo a brief conditioning procedure to recover the single-atom apex configuration prior to being subjected to operating conditions.

Single-atom Tip as an Emitter of Gas Field Ion Source

Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.