Microscopy and Microanalysis最新文献

Nanoparticles are utilized in a multitude of applications due to their unique properties. Consequently, characterization of nanoparticles is crucial, and various methods have been employed in these pursuits. One such method is Atom Probe Tomography (APT). However, existing sample preparation techniques for APT generally involve embedding of the nanoparticles in a matrix different from their environment in solutions or at solid-liquid interfaces. In this work, we demonstrate a methodology based on silica embedding and explore how it can be utilized to form a matrix for nanoparticles suitable for APT analysis. Through chemisorption to a surface, gold nanoparticles were densely packed, ensuring a high probability of encountering at least one particle in the APT analyses. The nanoparticle-covered surface was embedded in a silica film, replacing the water and thus making this method suitable for studying nanoparticles in their hydrated state. The nanoparticle's silver content and its distribution, originating from the nanoparticle synthesis, could be identified in the APT analysis. Sodium clusters, possibly originating from the sodium citrate used to stabilize the particles in solution, were observed on the nanoparticle surfaces. This indicates the potential for silica embedding to be used for studying ligands on nanoparticles in their hydrated state.

Atom probe tomography requires needle-shaped specimens with a diameter typically below 100 nm, making them both very fragile and reactive, and defects (notches at grain boundaries or precipitates) are known to affect the yield and data quality. The use of a conformal coating directly on the sharpened specimen has been proposed to increase yield and reduce background. However, to date, these coatings have been applied ex situ and mostly are not uniform. Here, we report on the controlled focused-ion beam in situ deposition of a thin metal film on specimens immediately after specimen preparation. Different metallic targets e.g. Cr were attached to a micromanipulator via a conventional lift-out method and sputtered using Ga or Xe ions. We showcase the many advantages of coating specimens from metallic to nonmetallic materials. We have identified an increase in data quality and yield, an improvement of the mass resolution, as well as an increase in the effective field-of-view. This wider field-of-view enables visualization of the entire original specimen, allowing to detect the complete surface oxide layer around the specimen. The ease of implementation of the approach makes it very attractive for generalizing its use across a very wide range of atom probe analyses.

Cryogenic atom probe tomography (cryo-APT) is being developed to enable nanoscale compositional analyses of frozen liquids. Yet, the availability of readily available substrates that allow for the fixation of liquids while providing sufficient strength to their interface is still an issue. Here, we propose the use of 1-2-µm-thick binary alloy film of gold-silver sputtered onto flat silicon, with sufficient adhesion without an additional layer. Through chemical dealloying, we successfully fabricate a nanoporous substrate, with an open-pore structure, which is mounted on a microarray of Si posts by lift-out in the focused-ion beam system, allowing for cryogenic fixation of liquids. We present cryo-APT results obtained after cryogenic sharpening, vacuum cryo-transfer, and analysis of pure water on the top and inside the nanoporous film. We demonstrate that this new substrate has the requisite characteristics for facilitating cryo-APT of frozen liquids, with a relatively lower volume of precious metals. This complete workflow represents an improved approach for frozen liquid analysis, from preparation of the films to the successful fixation of the liquid in the porous network, to cryo-APT.

Atom probe tomography (APT) is a unique analytical technique that offers three-dimensional elemental mapping with a spatial resolution down to the sub-nanometer. When APT is applied on complex heterogenous systems and/or under certain experimental conditions, that is, laser illumination, the specimen shape can deviate from an ideal hemisphere. Insufficient consideration of this aspect can introduce artifacts in the reconstructed dataset, ultimately degrading its spatial accuracy. So far, there has been limited investigation into the detailed evolution of emitter shape and its impact on the field-of-view (FOV). In this study, we numerically and experimentally investigated the FOV for asymmetric emitters and its evolution throughout the analysis depth. Our analysis revealed that, for asymmetric emitters, the ions evaporated from the topmost region of the specimen (summit) project approximately to the detector center. Furthermore, we demonstrated the implications of this finding on the FOV location for asymmetric emitters. Based on our findings, the location of the center of the FOV can deviate from the specimen central axis with an evolution depending on the evolution of the emitter shape. This study highlights the importance of accounting for the specimen shape when developing advanced data reconstruction schemes to enhance spatial resolution and accuracy.

The automation of the atom probe tomography (APT) tip preparation using a focused ion beam (FIB) with a scanning electron microscopy (SEM) dual-beam system will certainly contribute to systematic APT research with higher throughput and reliability. While our previous work established a method to prepare tips with a specified tip curvature and taper angle automatically, by using script-controlled FIB/SEM, the technique has been expanded to automated "site-specific" tip preparation in the current work. The improved procedure can automatically detect not only the tip shape but also the interface position in the tip; thus, the new function allows for control of the tip apex position. In other words, automated "site-specific" tip preparations are possible. The details of the automation procedure and some experimental demonstrations, that is, a Pt cap on Si, InGaN-based MQWs, and a p-n junction of GaAs, are presented.

Atom probe tomography data are composed of a list of coordinates of the reconstructed atoms in the probed volume. The elemental identity of each atom is derived from time-of-flight mass spectrometry, with no local chemical information readily available. In this study, we use a data processing technique referred to as field evaporation energy loss spectroscopy (FEELS), which analyzes the tails of mass peaks. FEELS was used to extract critical energetic parameters that are related to the activation energy for atoms to escape from the surface under intense electrostatic field and dependent of the path followed by the departing atoms. We focused our study on pure face-centered cubic metals. We demonstrate that the energetic parameters can be mapped in two-dimensional with nanometric resolution. A dependence on the considered crystallographic planes is observed, with sets of planes of low Miller indices showing a lower sensitivity to the field. The temperature is also an important parameter in particular for aluminum, which we attribute to an energetic transition between two paths of field evaporation between 25 and 60 K close to (002) pole. This paper shows that the information that can be retrieved from the measured energy loss of surface atoms is important both experimentally and theoretically.

Accurately controlling trace additives in dielectric barium titanate (BaTiO3) layers is important for optimizing the performance of multilayer ceramic capacitors (MLCCs). However, characterizing the spatial distribution and local concentration of the additives, which strongly influence the MLCC performance, poses a significant challenge. Atom probe tomography (APT) is an ideal technique for obtaining this information, but the extremely low electrical conductivity and piezoelectricity of BaTiO3 render its analysis with existing sample preparation approaches difficult. In this study, we developed a new APT sample preparation method involving W coating and heat treatment to investigate the trace additives in the BaTiO3 layer of MLCCs. This method enables determination of the local concentration and distribution of all trace elements in the BaTiO3 layer, including additives and undesired impurities. The developed method is expected to pave the way for the further optimization and advancement of MLCC technology.

The investigation of hydrogen in atom probe tomography appears as a relevant challenge due to its low mass, high diffusion coefficient, and presence as a residual gas in vacuum chambers, resulting in multiple complications for atom probe studies. Different solutions were proposed in the literature like ex situ charging coupled with cryotransfer or H charging at high temperature in a separate chamber. Nevertheless, these solutions often faced challenges due to the complex control of specimen temperature during hydrogen charging and subsequent analysis. In this paper, we propose an alternative route for in situ H charging in atom probe derived from a method developed in field ion microscopy. By applying negative voltage nanosecond pulse on the specimen in an atom probe chamber under a low pressure of H2, it is demonstrated that a high dose of H can be implanted in the range 2-20 nm beneath the specimen surface. An atom probe chamber was modified to enable direct negative pulse application with controlled gas pressure, pulse repetition rate, and pulse amplitude. Through electrodynamical simulations, we show that the implantation energy falls within the range 100-1,000 eV and a theoretical depth of implantation was predicted and compared to experiments.

Carbon fibers can play dual roles, carrying mechanical load and hosting lithium (Li) simultaneously in multifunctional devices called structural batteries. It is essential to gain a detailed understanding on the interaction between Li and carbon fibers on the nanoscale. Atom probe tomography (APT) can potentially reveal individual Li and C atoms. However, lithiated carbon fibers experience massive Li migration once exposed to the electric field in the APT instrument. We show that a few nanometers of a chromium (Cr) coating on APT specimens can shield the electric field and suppress the massive Li migration. The related effects of the Cr coating, such as introduction of oxygen, enhanced mass resolving power of the mass spectrum, and increased portion of single hits, are also discussed.

The present communication aims at demonstrating the wealth of information accessible by 1D-atom probe experiments using pulsed field desorption mass spectrometry (PFDMS), ultimately combined with video-field ion microscopy, while subjecting metallic samples to elevated gas pressures and studying surface reaction kinetics. Two case studies are being presented here: (a) the microkinetics of nickel tetracarbonyl (Ni(CO)4) formation through reaction of carbon monoxide with nickel and (b) the nitric oxide decomposition and reaction with hydrogen on platinum at variable steady electric fields mimicking electrocatalytic conditions. In both cases, surface areas with 140-150 atomic sites of the stepped Ni (001) and Pt (111) sample surfaces were probed. Under (a), we demonstrate variable repetition frequencies of field pulses to inform kinetic and mechanistic details of the surface reaction while under (b), we reveal the occurrence of field-induced processes impacting the surface reaction mechanism of nitric oxide with hydrogen and therefore opening new pathways not available under purely thermal conditions (in the absence of electric fields). Some aspects of PFDMS technical achievements will be discussed as they may provide clues for designing dynamic atom probe tomography instrumentation.