Beam-sample Interactions Research Articles

A low-kiloelectronvolt focused ion beam strategy for processing low-thermal-conductance materials with nanoampere currents.

Ion beam-induced heat damage in thermally low conductive specimens such as biological samples is gaining increased interest within the scientific community. This is partly due to the increased use of FIB-SEMs in biology as well as the development of complex materials, such as polymers, which need to be analyzed. The work presented here looks at the physics behind the ion beam-sample interactions and the effect of the incident ion energy (set by the acceleration voltage) on inducing increases in sample temperature and potential heat damage in thermally low conductive materials such as polymers and biological samples. The ion beam-induced heat for different ion beam currents at low acceleration voltages is calculated using Fourier's law of heat transfer, finite element simulations, and numerical modelling results and compared to experiments. The results indicate that with lower accelerator voltages, higher ion beam currents in the nanoampere range can be used to pattern or image soft material and non-resin-embedded biological samples with increased milling speed but reduced heat damage.

Exploration of Organic Nanomaterials with Liquid-Phase Transmission Electron Microscopy.

ConspectusOrganic, soft materials with solution-phase nanoscale structures, such as emulsions, hydrogels, and thermally responsive materials, are inherently difficult to directly image via dry state and cryogenic-transmission electron microscopy (TEM). Therefore, we lack a routine microscopy method with sufficient resolution that can, in tandem with scattering techniques, probe the morphology and dynamics of these and many related systems. These challenges motivate liquid cell (LC) TEM method development, aimed at making the technique generally available and routine. To date, the field has been and continues to be dominantly focused on analyzing solution-phase inorganic materials. These mostly metallic nanoparticles have been studied at electron fluxes that can allow for high-resolution imaging, in the range of hundreds to thousands of e- Å-2 s-1. Despite excellent contrast, in these cases, one often contends with knock-on damage, direct radiolysis, and sensitization of the solvent by virtue of enhanced secondary electron production by the impinging electron beam. With an interest in soft materials, we face both related and distinct challenges, especially in achieving a high-enough contrast within solvated liquid cells. Additionally, we must be aware of artifacts associated with high-flux imaging conditions in terms of direct radiolysis of the solvent and the sensitive materials themselves. Regardless, with care, it has become possible to gain real insight into both static and dynamic organic nanomaterials in solution. This is due, in large part, to key advances that have been made, including improved sample preparation protocols, image capture technologies, and image analysis, which have allowed LCTEM to have utility. To enable solvated soft matter characterization by LCTEM, a generalizable multimodal workflow was developed by leveraging both experimental and theoretical precedents from across the LCTEM field and adjacent works concerned with solution radiolysis and nanoparticle tracking analyses. This workflow consists of (1) modeling electron beam-solvent interactions, (2) studying electron beam-sample interactions via LCTEM coupled with post-mortem analysis, (3) the construction of "damage plots" displaying sample integrity under varied imaging and sample conditions, (4) optimized LCTEM imaging, (5) image processing, and (6) correlative analysis via X-ray or light scattering. In this Account, we present this outlook and the challenges we continue to overcome in the direct imaging of dynamic solvated nanoscale soft materials.

Electric Field-Induced Water Condensation Visualized by Vapor-Phase Transmission Electron Microscopy.

Understanding the nanoscale water condensation dynamics in strong electric fields is important for improving the atmospheric modeling of cloud dynamics and emerging technologies utilizing electric fields for direct air moisture capture. Here, we use vapor-phase transmission electron microscopy (VPTEM) to directly image nanoscale condensation dynamics of sessile water droplets in electric fields. VPTEM imaging of saturated water vapor stimulated condensation of sessile water nanodroplets that grew to a size of ∼500 nm before evaporating over a time scale of a minute. Simulations showed that electron beam charging of the silicon nitride microfluidic channel windows generated electric fields of ∼108 V/m, which depressed the water vapor pressure and effected rapid nucleation of nanosized liquid water droplets. A mass balance model showed that droplet growth was consistent with electric field-induced condensation, while droplet evaporation was consistent with radiolysis-induced evaporation via conversion of water to hydrogen gas. The model quantified several electron beam-sample interactions and vapor transport properties, showed that electron beam heating was insignificant, and demonstrated that literature values significantly underestimated radiolytic hydrogen production and overestimated water vapor diffusivity. This work demonstrates a method for investigating water condensation in strong electric fields and under supersaturated conditions, which is relevant to vapor-liquid equilibrium in the troposphere. While this work identifies several electron beam-sample interactions that impact condensation dynamics, quantification of these phenomena here is expected to enable delineating these artifacts from the physics of interest and accounting for them when imaging more complex vapor-liquid equilibrium phenomena with VPTEM.

Radiolysis-Driven Evolution of Gold Nanostructures - Model Verification by Scale Bridging In Situ Liquid-Phase Transmission Electron Microscopy and X-Ray Diffraction.

Utilizing ionizing radiation for in situ studies in liquid media enables unique insights into nanostructure formation dynamics. As radiolysis interferes with observations, kinetic simulations are employed to understand and exploit beam‐liquid interactions. By introducing an intuitive tool to simulate arbitrary kinetic models for radiation chemistry, it is demonstrated that these models provide a holistic understanding of reaction mechanisms. This is shown for irradiated HAuCl4 solutions allowing for quantitative prediction and tailoring of redox processes in liquid‐phase transmission electron microscopy (LP‐TEM). Moreover, it is demonstrated that kinetic modeling of radiation chemistry is applicable to investigations utilizing X‐rays such as X‐ray diffraction (XRD). This emphasizes that beam‐sample interactions must be considered during XRD in liquid media and shows that reaction kinetics do not provide a threshold dose rate for gold nucleation relevant to LP‐TEM and XRD. Furthermore, it is unveiled that oxidative etching of gold nanoparticles depends on both, precursor concentration, and dose rate. This dependency is exploited to probe the electron beam‐induced shift in Gibbs free energy landscape by analyzing critical radii of gold nanoparticles.

Modulating Electron Beam–Sample Interactions in Imaging and Diffraction Modes by Dose Fractionation with Low Dose Rates

Abstract Technological opportunities are explored to enhance detection schemes in transmission electron microscopy (TEM) that build on the detection of single-electron scattering events across the typical spectrum of interdisciplinary applications. They range from imaging with high spatiotemporal resolution to diffraction experiments at the window to quantum mechanics, where the wave-particle dualism of single electrons is evident. At the ultimate detection limit, where isolated electrons are delivered to interact with solids, we find that the beam current dominates damage processes instead of the deposited electron charge, which can be exploited to modify electron beam-induced sample alterations. The results are explained by assuming that all electron scattering are inelastic and include phonon excitation that can hardly be distinguished from elastic electron scattering. Consequently, a coherence length and a related coherence time exist that reflect the interaction of the electron with the sample and change linearly with energy loss. Phonon excitations are of small energy (<100 meV), but they occur frequently and scale with beam current in the irradiated area, which is why we can detect their contribution to beam-induced sample alterations and damage.

The combination of Raman microscopy and electron microscopy – Practical considerations of the influence of vacuum on Raman microscopy

Due to the specific vacuum requirements for scanning electron microscopy (SEM), the Raman microscope has to operate in vacuum in a correlative Raman-SEM, which is a type of microscope combination that has recently increased in popularity. This works considers the implications of conducting Raman microscopy under vacuum, as opposed to operating in ambient air, the standard working regime of this technique. We show that the performance of the optics of the Raman microscope are identical in both conditions, but laser beam-sample interactions, such as fluorescent bleaching and beam damage, might be different due to the lack of oxygen in vacuum. The bleaching of the fluorescent background appears to be mostly unaffected by the lack of oxygen, except when very low laser powers are used. Regarding laser-beam damage, organic samples are more sensitive in vacuum than in air, whereas no definite verdict is possible for inorganic samples. These findings have practical implications for the application of correlative Raman-SEM, as low laser powers, or in extreme cases cryo-methods, need to be used for organic samples that appear only moderately beam sensitive under usual ambient air.

Quantitative SEM-EDS Analysis of Semi-Transparent Samples

Abstract

Quantitative SEM-EDS Analysis of Semi-transparent Samples

Recent years have seen increased crossover of microscopy techniques developed for transmission electron microscopes (TEMs) being utilized as well in scanning electron microscopes (SEMs). The order of magnitude lower beam energies available in SEMs correspond with significantly different beam-sample interactions that must be accounted for when examining freestanding films. This is especially important for composition analysis via energy dispersive X-ray spectroscopy (EDS) since lower-energy transmission experiments mean X-ray volumes become comparable to sample dimensions. To better understand this scenario, we report results of an SEM-EDS study of terraced freestanding films comprising binary compounds with well-defined atomic ratios. Guided by Monte Carlo simulations, EDS line scan data were collected at different beam energies across segments of varying thicknesses. The results of quantification analysis using different models are compared for multiple combinations of beam energy, sample thickness, and material density, from which some general guidelines are provided for SEM-EDS analysis of freestanding films.

NanoFab SIMS: High Spatial Resolution Imaging and Analysis Using Inert-Gas Ion Beams

Abstract

Comment on, “On the influence of the electron dose-rate on the HRTEM image contrast”, by Juri Barthel, Markus Lentzen, Andreas Thust, ULTRAM12246 (2016), http://dx.doi.org/10.1016/j.ultramic.2016.11.016

• Typical electron dose rates that are used to capture single high resolution images induce atom (column) displacements that greatly exceed the average atom displacements calculated from Debye–Waller factors at room temperature. • The Born–Oppenheimer breaks down during the typical acquisition of high resolution images with beam current densities that greatly exceed 1000 e/Å 2 s. • A control of electron beam-sample interactions mandates reducing beam current densities down to single electrons/Å 2 s.

Measurement Error in Atomic-Scale Scanning Transmission Electron Microscopy-Energy-Dispersive X-Ray Spectroscopy (STEM-EDS) Mapping of a Model Oxide Interface.

With the development of affordable aberration correctors, analytical scanning transmission electron microscopy (STEM) studies of complex interfaces can now be conducted at high spatial resolution at laboratories worldwide. Energy-dispersive X-ray spectroscopy (EDS) in particular has grown in popularity, as it enables elemental mapping over a wide range of ionization energies. However, the interpretation of atomically resolved data is greatly complicated by beam-sample interactions that are often overlooked by novice users. Here we describe the practical factors-namely, sample thickness and the choice of ionization edge-that affect the quantification of a model perovskite oxide interface. Our measurements of the same sample, in regions of different thickness, indicate that interface profiles can vary by as much as 2-5 unit cells, depending on the spectral feature. This finding is supported by multislice simulations, which reveal that on-axis maps of even perfectly abrupt interfaces exhibit significant delocalization. Quantification of thicker samples is further complicated by channeling to heavier sites across the interface, as well as an increased signal background. We show that extreme care must be taken to prepare samples to minimize channeling effects and argue that it may not be possible to extract atomically resolved information from many chemical maps.

Detecting structural variances of Co3O4 catalysts by controlling beam-induced sample alterations in the vacuum of a transmission electron microscope.

This article summarizes core aspects of beam-sample interactions in research that aims at exploiting the ability to detect single atoms at atomic resolution by mid-voltage transmission electron microscopy. Investigating the atomic structure of catalytic Co3O4 nanocrystals underscores how indispensable it is to rigorously control electron dose rates and total doses to understand native material properties on this scale. We apply in-line holography with variable dose rates to achieve this goal. Genuine object structures can be maintained if dose rates below ~100 e/Å2s are used and the contrast required for detection of single atoms is generated by capturing large image series. Threshold doses for the detection of single atoms are estimated. An increase of electron dose rates and total doses to common values for high resolution imaging of solids stimulates object excitations that restructure surfaces, interfaces, and defects and cause grain reorientation or growth. We observe a variety of previously unknown atom configurations in surface proximity of the Co3O4 spinel structure. These are hidden behind broadened diffraction patterns in reciprocal space but become visible in real space by solving the phase problem. An exposure of the Co3O4 spinel structure to water vapor or other gases induces drastic structure alterations that can be captured in this manner.

On the pressing need to address beam–sample interactions in atomic resolution electron microscopy

Undeniably, the characterization of solids at the atomic scale using electron beams has become a core aspect of materials sciences. In fact, current abilities of advanced electron microscopes read like a fairy tale: Why not visualize the atomic structure of nanocrystals, defects, and surfaces? No problem, it can be done at a single atom level except for the detection of hydrogen atoms. Are you interested in the chemical composition of nanomaterials at the atomic scale? Atomically resolved maps of elemental distributions can be acquired before lunch, but it takes a little longer if you want to have them in three dimensions. Interested in property–function relationships? In situ microscopy will provide the needed solutions. In any case, ‘‘seeing is believing,’’ and one can trust the recorded images of atomic structures since they provide an artifactfree view of nature’s secrets and largely make obsolete the old-fashioned art of acquiring and interpreting low magnification images that often exhibit complex diffraction contrast. Certainly, advertisements for electron microscopes read like such tales, but reality must surely be different. Not at all! It is mind-buckling that the reality of forefront electron microscopy nowadays resides in the vicinity of such dream-like capabilities because recent technological advancements have placed electron microscopy into this spot. Never before in its distinguished history was the prospect for further improvements so rich. In fact, its impact reaches beyond materials sciences and

Does Your SEM Really Tell the Truth?-How Would You Know? Part 4: Charging and its Mitigation.

This is the fourth part of a series of tutorial papers discussing various causes of measurement uncertainty in scanned particle beam instruments, and some of the solutions researched and developed at NIST and other research institutions. Scanned particle beam instruments, especially the scanning electron microscope (SEM), have gone through tremendous evolution to become indispensable tools for many and diverse scientifc and industrial applications. These improvements have significantly enhanced their performance and made them far easier to operate. But, the ease of operation has also fostered operator complacency. In addition, the user-friendliness has reduced the apparent need for extensive operator training. Unfortunately, this has led to the idea that the SEM is just another expensive "digital camera" or another peripheral device connected to a computer and that all of the problems in obtaining good quality images and data have been solved. Hence, one using these instruments may be lulled into thinking that all of the potential pitfalls have been fully eliminated and believing that, everything one sees on the micrograph is always correct. But, as described in this and the earlier papers, this may not be the case. Care must always be taken when reliable quantitative data are being sought. The first paper in this series discussed some of the issues related to signal generation in the SEM, including instrument calibration, electron beam-sample interactions and the need for physics-based modeling to understand the actual image formation mechanisms to properly interpret SEM images. The second paper has discussed another major issue confronting the microscopist: specimen contamination and methods to eliminate it. The third paper discussed mechanical vibration and stage drift and some useful solutions to mitigate the problems caused by them, and here, in this the fourth contribution, the issues related to specimen "charging" and its mitigation are discussed relative to dimensional metrology.

Nanomanufacturing Concerns about Measurements Made in the SEM Part IV: Charging and its Mitigation.

This is the fourth part of a series of tutorial papers discussing various causes of measurement uncertainty in scanned particle beam instruments, and some of the solutions researched and developed at NIST and other research institutions. Scanned particle beam instruments especially the scanning electron microscope (SEM) have gone through tremendous evolution to become indispensable tools for many and diverse scientific and industrial applications. These improvements have significantly enhanced their performance and made them far easier to operate. But, the ease of operation has also fostered operator complacency. In addition, the user-friendliness has reduced the apparent need for extensive operator training. Unfortunately, this has led to the idea that the SEM is just another expensive "digital camera" or another peripheral device connected to a computer and that all of the problems in obtaining good quality images and data have been solved. Hence, one using these instruments may be lulled into thinking that all of the potential pitfalls have been fully eliminated and believing that, everything one sees on the micrograph is always correct. But, as described in this and the earlier papers, this may not be the case. Care must always be taken when reliable quantitative data are being sought. The first paper in this series discussed some of the issues related to signal generation in the SEM, including instrument calibration, electron beam-sample interactions and the need for physics-based modeling to understand the actual image formation mechanisms to properly interpret SEM images. The second paper has discussed another major issue confronting the microscopist: specimen contamination and methods to eliminate it. The third paper discussed mechanical vibration and stage drift and some useful solutions to mitigate the problems caused by them, and here, in this the fourth contribution, the issues related to specimen "charging" and its mitigation are discussed relative to dimensional metrology.

Observing Atoms at Work by Controlling Beam-Sample Interactions.

Functional behavior can be initiated and captured in series of images with previously unknown details using a successful effort to effectively control beam-sample interactions in high-resolution transmission electron microscopy. The approach uses tunable electron dose rates that can be chosen to be as low as attoamperes per square-Ångstrom to delay sample degradation to an unexplored end. Dose rates can be systematically increased to stimulate and observe dynamic object responses. Observations can be made in real time with deep sub-Ångstrom resolution and single-atom sensitivity, even if radiation-sensitive matter is probed and either pressure or temperature is raised in the electron microscope.

The Simulation of Energy Distribution of Electrons Detected by Segmental Ionization Detector in High Pressure Conditions of ESEM

AbstractThis paper presents computed dependencies of the detected electron energy distribution on the water vapour pressure in an environmental scanning electron microscope obtained using the EOD software with a Monte Carlo plug-in for the electron-gas interactions. The software GEANT was used for the Monte Carlo simulations of the beam-sample interactions and the signal electron emission from the sample into the gaseous environment. The simulations were carried out for selected energies of the signal electrons collected by two electrodes with two different diameters with the voltages of +350 V and 0, respectively, and then 0 and +350 V, respectively, and for the distance of 2 mm between the sample and the detection electrodes of the ionization detector. The simulated results are verified by experimental measurements. Consequences of the simulated and experimental dependencies on the acquisition of the topographical or material contrasts using our ionization detector equipped with segmented detection electrode are described and discussed.

ChemInform Abstract: Factors Influencing Quantitative Liquid (Scanning) Transmission Electron Microscopy

AbstractReview: 33 refs.

Factors influencing quantitative liquid (scanning) transmission electron microscopy

One of the experimental challenges in the study of nanomaterials in liquids in the (scanning) transmission electron microscope ((S)TEM) is gaining quantitative information. A successful experiment in the fluid stage will depend upon the ability to plan for sensitive factors such as the electron dose applied, imaging mode, acceleration voltage, beam-induced solution chemistry changes, and the specifics of solution reactivity. In this paper, we make use of a visual approach to show the extent of damage of different instrumental and experimental factors in liquid samples imaged in the (S)TEM. Previous results as well as new insights are presented to create an overview of beam-sample interactions identified for changing imaging and experimental conditions. This work establishes procedures to understand the effect of the electron beam on a solution, provides information to allow for a deliberate choice of the optimal experimental conditions to enable quantification, and identifies the experimental factors that require further analysis for achieving fully quantitative results in the liquid (S)TEM.

Beam-Sample Interactions During Liquid Cell Electron Microscopy

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