Sharp Tungsten Tip Research Articles

Precisely Picking Nanoparticles by a "Nano-Scalpel" for 360° Electron Tomography.

Electron tomography (ET) has gained increasing attention for the 3D characterization of nanoparticles. However, the missing wedge problem due to a limited tilt angle range is still the main challenge for accurate reconstruction in most experimental TEM setups. Advanced algorithms could in-paint or compensate to some extent the missing wedge artifacts, but cannot recover the missing structural information completely. 360° ET provides an option to solve this problem by tilting a needle-shaped specimen over the full tilt range and thus filling the missing information. However, sample preparation especially for fine powders to perform full-range ET is still challenging, thus limiting its application. In this work, we propose a new universal sample preparation method that enables the transfer of selected individual nanoparticle or a few separated nanoparticles by cutting a piece of carbon film supporting the specimen particles and mounting them onto the full-range tomography holder tip with the help of an easily prepared sharp tungsten tip. This method is demonstrated by 360° ET of Pt@TiO2 hollow cage catalyst showing high quality reconstruction without missing wedge.

In Situ Manipulation and Micromechanical Characterization of Diatom Frustule Constituents Using Focused Ion Beam Scanning Electron Microscopy.

Biocomposite structures are difficult to characterize by bulk approaches due to their morphological complexity and compositional heterogeneity. Therefore, a versatile method is required to assess, for example, the mechanical properties of geometrically simple parts of biocomposites at the relevant length scales. Here, it is demonstrated how a combination of Focused Ion Beam Scanning Electron Microscopy (FIB-SEM) and micromanipulators can be used to isolate, transfer, and determine the mechanical properties of frustule constituents of diatom Thalassiosira pseudonana (T.p.). Specifically, two parts of the diatom frustule, girdle bands and valves, are separated by FIB milling and manipulated using a sharp tungsten tip without compromising their physical or chemical integrity. In situ mechanical studies on isolated girdle bands combined with Finite Element Method (FEM) simulations, enables the quantitative assessment of the Young's modulus of this biosilica; E= 40.0GPa. In addition, the mechanical strength of isolated valves could be measured by transferring and mounting them on top of premilled holes in the sample support. This approach may be extended to any hierarchical biocomposite material, regardless of its chemical composition, to isolate, transfer, and investigate the mechanical properties of selected constituents or specific regions.

Development and Comparative Analysis of Electrochemically Etched Tungsten Tips for Quartz Tuning Fork Sensor.

Quartz Tuning Fork (QTF) based sensors are used for Scanning Probe Microscopes (SPM), in particular for near-field scanning optical microscopy. Highly sharp Tungsten (W) tips with larger cone angles and less tip diameter are critical for SPM instead of platinum and iridium (Pt/Ir) tips due to their high-quality factor, conductivity, mechanical stability, durability and production at low cost. Tungsten is chosen for its ease of electrochemical etching, yielding high-aspect ratio, sharp tips with tens of nanometer end diameters, while using simple etching circuits and basic electrolyte chemistry. Moreover, the resolution of the SPM images is observed to be associated with the cone angle of the SPM tip, therefore Atomic-Resolution Imaging is obtained with greater cone angles. Here, the goal is to chemically etch W to the smallest possible tip apex diameters. Tips with greater cone angles are produced by the custom etching procedures, which have proved superior in producing high quality tips. Though various methods are developed for the electrochemical etching of W wire, with a range of applications from scanning tunneling microscopy (SPM) to electron sources of scanning electron microscopes, but the basic chemical etching methods need to be optimized for reproducibility, controlling cone angle and tip sharpness that causes problems for the end users. In this research work, comprehensive experiments are carried out for the production of tips from 0.4 mm tungsten wire by three different electrochemical etching techniques, that is, Alternating Current (AC) etching, Meniscus etching and Direct Current (DC) etching. Consequently, sharp and high cone angle tips are obtained with required properties where the results of the W etching are analyzed, with optical microscope, and then with field emission scanning electron microscopy (FE-SEM). Similarly, effects of varying applied voltages and concentration of NaOH solution with comparison among the produced tips are investigated by measuring their cone angle and tip diameter. Moreover, oxidation and impurities, that is, removal of contamination and etching parameters are also studied in this research work. A method has been tested to minimize the oxidation on the surface and the tips were characterized with scanning electron microscope (SEM).

Manipulation Technique for Precise Transfer of Single Perovskite Nanoparticles.

In this article, we present the pick-and-place technique for the manipulation of single nanoparticles on non-conductive substrates using a tungsten tip irradiated by a focused electron beam from a scanning electron microscope. The developed technique allowed us to perform the precise transfer of single BaTiO3 nanoparticles from one substrate to another in order to carry out measurements of elastic light scattering as well as second harmonic generation. Also, we demonstrate a fabricated structure made by finely tuning the position of a BaTiO3 nanoparticle on top of a dielectric nanowaveguide deposited on a glass substrate. The presented technique is based on the electrostatic interaction between the sharp tungsten tip charged by the electron beam and the nanoscale object. A mechanism for nanoparticle transfer to a non-conductive substrate is proposed and the forces involved in the manipulation process are evaluated. The presented technique can be widely utilized for the fabrication of nanoscale structures on optically transparent non-conductive substrates, which presents a wide range of applications for nanophotonics.

Shaping nanomaterials by short electrical pulses

We report a new dry-state technique for non-contact patterning of nanostructured conducting materials, and demonstrate its use for carbon nanotube forests and freestanding sheets of carbon nanotubes, graphene, graphene sponge, and MXene. This method uses self-generated electron-emission pulses (∼20 ns) in air. On a substrate—tip separation scale of 10 to 20 nm, the few molecules of gas at atmospheric pressure enables electron-emission-based interaction between a sharp tungsten tip and elements of nanostructured materials. Using the advantages of field enhancement at sharp ends of nanostructured materials, the discharge voltage is reduced to 25–30 V, depending upon the materials density. This method causes largely non-oxidative sequential decomposition of nanostructure elements neighboring the tungsten tip. The main decomposition mechanism is thermal dissociation facilitated by Joule heating and electrostatic removal of debris. The non-contact-based patterning of nanomaterials can be as fast as 10 cm s−1. The resulting precisely patterned structures (<200 nm) are largely free of foreign contaminants, thermal impact and sub-surface structural changes.

A two-dimensional structure graphene STM tips fabricated by microwave plasma enhanced chemical vapor deposition

The atomic edge, excellent conductivity, stable chemical and mechanical properties make graphene a good candidate for the scanning tunneling microscopy (STM) tip. Here, a one-step growth method is used to fabricate graphene STM tips. The graphene was directly grown on a sharp tungsten tip vertically by using microwave plasma enhanced chemical vapor deposition method without any catalyst. The high resolution TEM image demonstrated that inert W2C layer was formed at the surface of tungsten during growth which can protect the oxidation of tungsten tip and promote the electric conductivity of graphene STM tip of 4000 times than the oxidative tungsten tip. The in situ TEM field evaporation experiments revealed that the graphene has a good stability under high electric field of 24.7 V/nm. Using the graphene STM tip, atomic resolution images of highly oriented pyrolytic graphite and tungsten disulfide were obtained. Our experiment results demonstrated the graphene STM tip was available to get atomic resolution image for at least one week. It is a promising approach to fabricate STM tips for high resolution imaging in a fast and economical way.

Laser-induced asymmetric faceting and growth of a nano-protrusion on a tungsten tip

Irradiation of a sharp tungsten tip by a femtosecond laser and exposed to a strong DC electric field led to reproducible surface modifications. By a combination of field emission microscopy and scanning electron microscopy, we observed asymmetric surface faceting with sub-ten nanometer high steps. The presence of faceted features mainly on the laser-exposed side implies that the surface modification was driven by a laser-induced transient temperature rise on a scale of a couple of picoseconds in the tungsten tip apex. Moreover, we identified the formation of a nano-tip a few nanometers high located at one of the corners of a faceted plateau. The results of simulations emulating the experimental conditions are consistent with the experimental observations. The presented technique would be a new method to fabricate a nano-tip especially for generating coherent electron pulses. The features may also help to explain the origin of enhanced field emission, which leads to vacuum arcs, in high electric field devices such as radio-frequency particle accelerators.

Field emission analysis of band bending in donor/acceptor heterojunction

The donor/acceptor heterojunction plays an important role in organic solar cells. An investigation of band bending in the donor/acceptor heterojunction is helpful in analysis of the charge transport behavior and for the improvement of the device performance. In this work, we report an approach for detection of band bending in a donor/acceptor heterojunction that has been prepared on a small and sharp tungsten tip. In situ field emission measurements are performed after the deposition process, and a linear Fowler-Nordheim plot is obtained from the fresh organic film surface. The thickness-dependent work function is then measured in the layer-by-layer deposited heterojunction. Several different types of heterojunction (zinc phthalocyanine (ZnPc)/C60, copper phthalocyanine (CuPc)/3,4,9,10-perylenetetracarboxylic bisbenzimidazole, and CuPc/C60) are fabricated and analyzed. The different charge transfer directions in the heterojunctions are distinguished by field emission measurements. The calculation method used to determine the band bending is then discussed in detail. A triple layer heterojunction (C60/ZnPc/CuPc) is also analyzed using this method. A small amount of band bending is measured in the outer CuPc layer. This method provides an independent reference method for determination of the band bending in an organic heterojunction that will complement photoemission spectroscopy and current-voltage measurement methods.

A Scanning Probe Microscope for Surface Measurement in Nano-Scale.

A tapping mode scanning probe microscopy (TM SPM) system for surface measurement in nanoscale is developed, of which the main element is a scanning probe consisting of quartz tuning fork and a long sharp tungsten tip. Quartz tuning fork is a very good resonant element with piezoelectrical characteristic, and it acts as an actuator and a force sensor simultaneously in the probe. The vertical spatial resolution of the TM SPM is up to sub-nanometer (0.11 nm) and the measuring force is in micro Newton magnitude (about 30 μN). In the scanning operation, the probe vibrates at its resonant frequency, so that the amplitude or frequency (or phase) of the resonant tuning fork is very sensitive to external forces (Its quality factor in air is about 3138). Using the TM SPM constructed by this probe, silicon samples are scanned. Their topography and phase images which indicate the surface material characteristics are reconstructed effectively with a high resolution and low destructiveness. Soft materials, such as Protein structure can also be scanned theoretically without damage. In addition, because of the using of the long sharp tungsten tip, the system has the capacity of measuring micro structures with large aspect ratio, such as large micro steps, deep micro trenches, etc.

Ultrafast Time-Resolved Photoelectric Emission.

The emission times of laser-triggered electrons from a sharp tungsten tip are directly characterized under ultrafast, near-infrared laser excitation at Keldysh parameters of 6.6<γ<19.1. Emission delays up to 10fs are observed, which are inferred from the energy gain of photoelectrons emitted into a synchronously driven microwave cavity. Few femtosecond timing resolution is achieved in a configuration capable of measuring timing shifts up to 55ps. The technique can also be used to measure the microwave phase inside the cavity with a precision below 70fs upon the energy resolved detection of a single electron.

All-Diamond Microelectrodes as Solid State Probes for Localized Electrochemical Sensing

The fabrication of an all-diamond microprobe is demonstrated for the first time. This ME (microelectrode) assembly consists of an inner boron doped diamond (BDD) layer and an outer undoped diamond layer. Both layers were grown on a sharp tungsten tip by chemical vapor deposition (CVD) in a stepwise manner within a single deposition run. BDD is a material with proven potential as an electrochemical sensor. Undoped CVD diamond is an insulating material with superior chemical stability in comparison to conventional insulators. Focused ion beam (FIB) cutting of the apex of the ME was used to expose an electroactive BDD disk. By cyclic voltammetry, the redox reaction of ferrocenemethanol was shown to take place at the BDD microdisk surface. In order to ensure that the outer layer was nonelectrically conductive, a diffusion barrier for boron atoms was established seeking the formation of boron-hydrogen complexes at the interface between the doped and the undoped diamond layers. The applicability of the microelectrodes in localized corrosion was demonstrated by scanning amperometric measurements of oxygen distribution above an Al-Cu-CFRP (Carbon Fiber Reinforced Polymer) galvanic corrosion cell.

Tip radius quantification using feature-size mapping of field ion microscopy images

We are presenting a rapid and straightforward approach to determine the tip radius of sharp tungsten tips characterized by field ion microscopy. The utilization of certain features with well-known dimensions on the surface of these tips around the crystallographic [111] direction allows us to increase the accuracy of the radius measurement by almost one order of magnitude in comparison to standard methods. By employing a few reasonable approximations, it is possible to derive an analytical expression for the tip radius as a function of the observed feature size on the microchannel plate and some geometric parameters of the setup. Finally, we show that field ion microscopy images can be reconstructed on the atomic level by using a perfect hemisphere with the determined radius as a starting value and a low number of modifications in the topmost surface layers. In particular, this is useful for quantifying tip-sample interactions and characterizing material properties in atomic force microscopy.

Nonlinear femtosecond laser induced scanning tunneling microscopy

We demonstrate ultrafast laser driven nonlinear scanning tunneling microscopy (STM), under ambient conditions. The design is an adaptation of the recently introduced cross-polarized double beat method, whereby z-polarized phase modulated fields are tightly focused at a tunneling junction consisting of a sharp tungsten tip and an optically transparent gold film as substrate. We demonstrate the prerequisites for ultrafast time-resolved STM through an operative mechanism of nonlinear laser field-driven tunneling. The spatial resolution of the nonlinear laser driven STM is determined by the local field intensity. Resolution of 0.3 nm-10 nm is demonstrated for the intensity dependent, exponential tunneling range. The demonstration is carried out on a junction consisting of tungsten tip and gold substrate. Nano-structured gold is used for imaging purposes, to highlight junction plasmon controlled tunneling in the conductivity limit.

Semiconducted symphony: ultrafast field emitter array

Semiconducted symphony: ultrafast field emitter array

Imaging Joule Heating in an 80 nm Wide Titanium Nanowire by Thermally Modulated Fluorescence

A fluorescent erbium/ytterbium co-doped fluoride nanocrystal glued at the end of a sharp atomic force microscope tungsten tip was used as a nanoscale thermometer. The thermally induced fluorescence quenching enabled observation of the heating and measurement of the temperature distribution in a Joule-heated 80 nm wide and 2 μm long titanium nanowire fabricated on an oxidized silicon substrate. The measurements have been carried out in an alternating heating mode by applying a modulated current on the device at low frequency. The heating is found to be inhomogeneous along the wire, and the temperature in its center increases quadratically with the applied current. Heat appears to be confined mainly along the wire, with weak lateral diffusion along the substrate and in the lateral metallic pads. The lateral resolution of this thermal measurement technique is better than 250 nm. It could also be used to study thermally induced defects in nanodevices.

Refined tip preparation by electrochemical etching and ultrahigh vacuum treatment to obtain atomically sharp tips for scanning tunneling microscope and atomic force microscope

A modification of the common electrochemical etching setup is presented. The described method reproducibly yields sharp tungsten tips for usage in the scanning tunneling microscope and tuning fork atomic force microscope. In situ treatment under ultrahigh vacuum (p ≤10(-10) mbar) conditions for cleaning and fine sharpening with minimal blunting is described. The structure of the microscopic apex of these tips is atomically resolved with field ion microscopy and cross checked with field emission.

Note: A scanning thermal probe microscope that operates in liquids

We have developed a scanning thermal probe microscope that operates in liquid environments. The thermal sensor is a fluorescent particle glued at the end of a sharp tungsten tip. Since light emission is a strongly thermally sensitive effect, the measurement of the particle fluorescence variations allows the determination of the temperature. No electrical wiring of the probe is needed. As a demonstrative example, we have measured the temperature map of a Joule-heated microheater immersed in a water∕glycerol solution. Both topographical and thermal images are obtained with a good sensitivity.

Electrospraying insulating liquids via charged nanodrop injection from the Taylor cone of an ionic liquid

Charge is injected into the bulk of an insulating liquid in the form of nanodrops produced by an immersed Taylor cone of an ionic liquid. The charge then drifts onto the insulator surface, destabilizing it and leading to the formation of an electrified jet that atomizes into approximately monodisperse micron size insulator drops. The approach is similar to those previously based on field injection of ions from sharp tungsten tips, but the continuous renewal and self-sharpening of the liquid charge-injector permits long-term stable operation. Using heptane as the insulator and 1-ethyl-3-methylimidazolium-BF4 as the ionic liquid we produce approximately monodisperse drops with average diameters ranging from less than 4 up to 20 μm, injecting in some cases as little as 0.0002% by volume of ionic liquid. No fundamental limitation restricting the possibility of forming even smaller drops is apparent. The scaling law of Kim and Turnbull [“Generation of charged drops of insulating liquids by electrostatic spraying,” J. Appl. Phys. 47, 1964 (1976)] where the drop diameter varies as the 2/3 power of the liquid flow rate and the −2/3 power of the spray current is confirmed, implying that the drops are on the average charged to 50%–60% of the Rayleigh limit.

Fast coating of ultramicroelectrodes with boron-doped nanocrystalline diamond

The present work is focused on the deposition of thin boron-doped nanocrystalline diamond (B-NCD) films on electrochemically etched tungsten wires by the hot filament assisted CVD method. The goal is the manufacturing of robust inert ultramicroelectrodes (UMEs) with a superior performance to be used for localised electrochemical analysis. The conductive diamond films can confer high stability of chemical and physical properties as well as low background current. Filament and substrate temperatures were kept constant at 2350 °C and 670 °C, respectively. The total system pressure was equal to 50 mbar and the CH 4/H 2 gas flow ratio was 0.07. Boron was used as the doping agent by solving B 2O 3 in ethanol, with a B/C content of 15000 ppm, and the solution was then dragged with argon gas flowing through a bubbler. The (Ar+B)/H 2 ratio values varied within the range of 0.06–0.21. The film growth rate decreases with the boron content increasing, but larger (Ar+B)/H 2 ratios result in smoother surfaces. UMEs insulation was carried out with epoxy resin in a home built device. The production of very sharp tungsten tips fully coated with B-NCD after just 30 min, for a (Ar+B)/H 2 ratio of 0.21, is one of the main outcomes of this work. The cyclic voltammetry showed a stable behavior with a wide electrochemical window of ~ 2.25 V in a 0.05 M NaCl solution proving the applicability of the developed UME for localized electroanalytical studies in biomedical and corrosion applications.

Metastable Helium Molecules as Tracers in SuperfluidHe4

Metastable helium molecules generated in a discharge near a sharp tungsten tip immersed in superfluid 4He are imaged using a laser-induced-fluorescence technique. By pulsing the tip, a small cloud of He(2*) molecules is produced. We can determine the normal-fluid velocity in a heat-induced counterflow by tracing the position of a single molecule cloud. As we run the tip in continuous field-emission mode, a normal-fluid jet from the tip is generated and molecules are entrained in the jet. A focused 910 nm pump laser pulse is used to drive a small group of molecules to the first excited vibrational level of the triplet ground state. Subsequent imaging of the tagged molecules with an expanded 925 nm probe laser pulse allows us to measure the flow velocity of the jet. The techniques we developed provide new tools in quantitatively studying the normal fluid flow in superfluid helium.