Secondary-electron imaging of bulk crystalline specimens in an aberration corrected STEM.

Atomic-scale electron microscopy traditionally probes thin specimens, with thickness below 100 nm, and its feasibility for bulk samples has not been documented. In this study, we explore the practicality of scanning transmission electron microscope (STEM) imaging with secondary electrons (SE), using a silicon-wedge specimen having a maximum thickness of 18 µm. We find that the atomic structure is present in the entire thickness range of the SE images although the background intensity increases moderately with thickness. The consistent intensity of secondary electron (SE) images at atomic positions and the modest increase in background intensity observed in silicon suggest a limited contribution from SEs generated by backscattered electrons, a conclusion supported by our multislice calculations. We conclude that achieving atomic resolution in SE imaging for bulk specimens is indeed attainable using aberration-corrected STEM and an aberration-corrected scanning electron microscope (SEM) may have the capacity for atomic-level resolution, holding great promise for future strides in materials research.

Nonequilibrium Dynamics of Electron Emission from Cold and Hot Graphene under Proton Irradiation.

Characteristic properties of secondary electrons emitted from irradiated two-dimensional materials arise from multi-length and multi-time-scale relaxation processes that connect the initial nonequilibrium excited electron distribution with their eventual emission. To understand these processes, which are critical for using secondary electrons as high-resolution thermalization probes, we combine first-principles real-time electron dynamics with irradiation experiments. Our data for cold and hot proton-irradiated graphene show signatures of kinetic and potential emission and generally good agreement for electron yields between experiment and theory. The duration of the emission pulse is about 1.5 fs, which indicates high time resolution when used as a probe. Our newly developed method to predict kinetic energy spectra shows good agreement with electron and ion irradiation experiments and prior models. We find that the lattice temperature significantly increases secondary electron emission, whereas electron temperature has a negligible effect.

High-Throughput Morphological Chirality Quantification of Twisted and Wrinkled Gold Nanorods.

Chirality in gold nanostructures offers an exciting opportunity to tune their differential optical response to left- and right-handed circularly polarized light, as well as their interactions with biomolecules and living matter. However, tuning and understanding such interactions demands quantification of the structural features that are responsible for the chiral behavior. Electron tomography (ET) enables structural characterization at the single-particle level and has been used to quantify the helicity of complex chiral nanorods. However, the technique is time-consuming and consequently lacks statistical value. To address this issue, we introduce herein a high-throughput methodology that combines images acquired by secondary electron-based electron beam-induced current (SEEBIC) with quantitative image analysis. As a result, the geometric chirality of hundreds of nanoparticles can be quantified in less than 1 h. When combining the drastic gain in data collection efficiency of SEEBIC with a limited number of ET data sets, a better understanding of how the chiral structure of individual chiral nanoparticles translates into the ensemble chiroptical response can be reached.

Simultaneous secondary electron microscopy in the scanning transmission electron microscope with applications for in situ studies.

Scanning/transmission electron microscopy (STEM) is a powerful characterization tool for a wide range of materials. Over the years, STEMs have been extensively used for in situ studies of structural evolution and dynamic processes. A limited number of STEM instruments are equipped with a secondary electron (SE) detector in addition to the conventional transmitted electron detectors, i.e. the bright-field (BF) and annular dark-field (ADF) detectors. Such instruments are capable of simultaneous BF-STEM, ADF-STEM and SE-STEM imaging. These methods can reveal the 'bulk' information from BF and ADF signals and the surface information from SE signals for materials <200 nm thick. This review first summarizes the field of in situ STEM research, followed by the generation of SE signals, SE-STEM instrumentation and applications of SE-STEM analysis. Combining with various in situ heating, gas reaction and mechanical testing stages based on microelectromechanical systems (MEMS), we show that simultaneous SE-STEM imaging has found applications in studying the dynamics and transient phenomena of surface reconstructions, exsolution of catalysts, lunar and planetary materials and mechanical properties of 2D thin films. Finally, we provide an outlook on the potential advancements in SE-STEM from the perspective of sample-related factors, instrument-related factors and data acquisition and processing.

A calculation approach for current density distribution evolution of secondary electrons using differential algebra method.

In this study, the concept of the current density distribution (CDD) evolution of secondary electron (SE) beam is presented, and a novel approach using the differential algebra (DA) method is proposed to calculate the CDD evolution of the SE beam. Firstly, the emitted SE beam is divided into some beamlets in polar and azimuth angle directions. For each beamlet only one reference trajectory is traced using DA method. As a result, the transfer properties for this beamlet are obtained. Using the transfer properties, the current density function at arbitrary plane for the beamlet can be derived, in which the initial angle distribution, energy distribution and emission source size are considered. And then, the current density function is integrated, resulting in the CDD of this beamlet at arbitrary plane. Finally, the CDD evolution of the whole SE beam is obtained by superposing the CDDs of all beamlets. As an example, a SE detection system for a scanning electron microscope (SEM) is calculated using the proposed approach and therefore the SE CDD evolution is obtained and analyzed. Furthermore, experiments for observing the SE image of detector are performed, and the calculated SE CDD and the corresponding simulation images well explained the experimental results, validating the proposed calculation method. The proposed approach can be potentially applied for optimizing the SE detection system and therefore improving the collection efficiency of SE.

Prediction of secondary electron yield for metal materials using deep learning.

This article describes a neural network system for predicting the secondary electron yield of metallic materials. For bulk metals, experimental values are used as training data. Due to the strong correlation between the secondary electron yield and the work function, deep learning predicts the secondary electron yield with relatively high accuracy even with a small amount of training data. Our approach demonstrates the importance of the work function in predicting the secondary electron yield. For the secondary electron yield of thin metal films on metal substrates, deep learning predictions are generated using training data obtained by Monte Carlo simulations. The accuracy of the secondary yield predictions of thin films on substrates could be improved by adding experimental values of bulk metals to the training data.

Design and optimization of a conical electrostatic objective lens of a low-voltage scanning electron microscope for surface imaging and analysis in ultra-high-vacuum environment.

Low-voltage scanning electron microscopy (LV-SEM) with landing energies below 5 keV has been widely used due to its advantages in mitigating the damage and charging effects to a specimen and enhancing surface information due to small interaction volume of electrons inside a specimen. Additionally, for elemental analysis of the surfaces of bulk specimens with Auger electron spectroscopy (AES) or electron energy loss spectroscopy (EELS), ultra-high-vacuum (UHV) environment is essential to maintain clean surfaces without the absorption of gas molecules during the electron beam irradiation for the acquisition of spectral data. In this study, we propose the optimal design and condition of a conical Electrostatic Objective Lens (EOL) for a UHV LV-SEM to achieve the high spatial resolution and secondary electron (SE) detection efficiency. The EOL is composed of only the three electrodes (retarding, focusing and booster electrodes) and the insulators, which is suitable for maintaining a UHV environment with less out-gassing. The cone angle of the EOL is determined as 60° to integrate a spectrometer in the UHV LV-SEM and in a large size and a higher tilt angle of the sample. Through the optimization with the simulations, the EOL achieves the minimized spherical and chromatic aberration coefficients of 0.05 and 0.03 mm at the sample side, respectively, at the landing energy of 50 eV and the shortest working distance (WD) of 1 mm for high-resolution imaging. In addition, the probe diameter of the optimized EOL is 2.3 nm at 1 keV and 5.7 nm at 50 eV with a WD of 1 mm and a probe current of 10 pA, which are comparable to previously studied compound objective lenses with magnetic and electrostatic lenses. Using a longer WD of 4 mm for analysis, the probe diameter was 5.4 nm at 1 keV and the SE detection efficiency was 83.3 % owing to the separated scintillator detector structure from the booster electrode. These results imply that the optimized EOL has the potential to be applied to a high-performance UHV LV-SEM for the surface imaging and analysis with a simple system configuration.

Electron holography observation of electron spin polarization around charged insulating wire.

We report direct observation by electron holography of the spin polarization of electrons in a vacuum region around a charged SiO2 wire coated with Pt-Pd. Irradiating the SiO2 wire with 300-keV electrons caused the wire to become positively charged due to the emission of secondary electrons. The spin polarization of these electrons interacting with the charged wire was observed in situ using a phase reconstruction process under an external magnetic field. The magnetic field of the spin-polarized electrons was simulated taking into account the distribution of secondary electrons and the effect of the external magnetic field.

Suppression of Secondary Electron Emission from Nickel Surface by Graphene Composites Based on First-Principles Method.

Secondary electron emission (SEE) is a fundamental phenomenon of particle/surface interaction, and the multipactor effect induced by SEE can result in disastrous impacts on the performance of microwave devices. To suppress the SEE-induced multipactor, an Ni (111) surface covered with a monolayer of graphene was proposed and studied theoretically via the density functional theory (DFT) method. The calculation results indicated that redistribution of the electron density at the graphene/Ni (111) interface led to variations in the work function and the probability of SEE. To validate the theoretical results, experiments were performed to analyze secondary electron yield (SEY). The measurements showed a significant decrease in the SEY on an Ni (111) surface covered with a monolayer of graphene, accompanied by a decrease in the work function, which is consistent with the statistical evidence of a strong correlation between the work function and SEY of metals. A discussion was given on explaining the experimental phenomenon using theoretical calculation results, where the empty orbitals lead to an electron trapping effect, thereby reducing SEY.

Tailoring Organic/Inorganic Interface Trap States of Metal Oxide/Polyimide toward Improved Vacuum Surface Insulation.

High-voltage and high-power devices are indispensable in spacecraft for outer space explorations, whose operations require aerospace materials with adequate vacuum surface insulation performance. Despite persistent attempts to fabricate such materials, current efforts are restricted to trial-and-error methods and a universal design guideline is missing. The present work proposes to improve the vacuum surface insulation by tailoring the surface trap state density and energy level of the metal oxides with varied bandgaps, using coating on a polyimide (PI) substrate, aiming for a more systematical workflow for the insulation material design. First-principle calculations and trap diagnostics are employed to evaluate the material properties and reveal the interplay between trap states and the flashover threshold, supported by dedicated analyses of the flashover voltage, secondary electron emission (SEE) from insulators, and surface charging behaviors. Experimental results suggest that the coated PI (i.e., CuO@PI, SrO@PI, MgO@PI, and Al2O3@PI) can effectively increase the trap density and alter the trap energy levels. Elevated trap density is demonstrated to always yield lower SEE. In addition, increasing shallow trap density accelerates surface charge dissipation, which is favorable for improving surface insulation. CuO@PI exhibits the most remarkable increase in shallow trap density, and accordingly, the highest flashover voltage is 42.5% higher than that of pristine PI. This study reveals the critical role played by surface trap states in flashover mitigation and offers a novel strategy to optimize the surface insulation of materials.

Assessing the Quality of Oxygen Plasma Focused Ion Beam (O-PFIB) Etching on Polypropylene Surfaces Using Secondary Electron Hyperspectral Imaging.

The development of Focused Ion Beam-Scanning Electron Microscopy (FIB-SEM) systems has provided significant advances in the processing and characterization of polymers. A fundamental understanding of ion-sample interactions is still missing despite FIB-SEM being routinely applied in microstructural analyses of polymers. This study applies Secondary Electron Hyperspectral Imaging to reveal oxygen and xenon plasma FIB interactions on the surface of a polymer (in this instance, polypropylene). Secondary Electron Hyperspectral Imaging (SEHI) is a technique housed within the SEM chamber that exhibits multiscale surface sensitivity with a high spatial resolution and the ability to identify carbon bonding present using low beam energies without requiring an Ultra High Vacuum (UHV). SEHI is made possible through the use of through-the-lens detectors (TLDs) to provide a low-pass SE collection of low primary electron beam energies and currents. SE images acquired over the same region of interest from different energy ranges are plotted to produce an SE spectrum. The data provided in this study provide evidence of SEHI's ability to be a valuable tool in the characterization of polymer surfaces post-PFIB etching, allowing for insights into both tailoring polymer processing FIB parameters and SEHI's ability to be used to monitor serial FIB polymer surfaces in situ.

Study of TiO2 on the Voltage Holdoff Capacity of Cr/Mn-Doped Al2O3 Ceramic in Vacuum.

With the development of vacuum electronic devices toward high power, high frequency, and miniaturization, the voltage holdoff capacity of the insulation materials in devices has also been raised to a higher demand. Cr/Mn/Ti-doped Al2O3 ceramics were prepared, and the bulk density, micromorphology, phase composition, resistivity, secondary electron emission coefficient, and surface flashover threshold in the vacuum of the Al2O3 were characterized. The results show that the addition of TiO2 to the Al2O3 ceramic can promote the sintering of the ceramic. The Cr/Mn/Ti-doped Al2O3 ceramic with a homogeneous microstructure can be obtained by an appropriate amount of TiO2 addition. In the process of the heat treatment, the TiO2 in the ceramics was reduced to a certain degree, which had an impact on the microstructure of the Al2O3 ceramic. Adding a small amount of TiO2 can improve the voltage holdoff performance in the vacuum. The value of the surface flashover threshold in the vacuum of the Cr/Mn/Ti-doped Al2O3 ceramic containing 1 wt.% TiO2 reached a value of 33 kV, which is 32% higher than that of the basic Al2O3 ceramic. The preparation of Al2O3 ceramics with a high voltage holdoff capacity in a vacuum provides fundamental technical support for the development of vacuum electronic devices.

Mean Free Path of Electrons in Organic Photoresists for Extreme Ultraviolet Lithography in the Kinetic Energy Range 20-450 eV.

The blur caused by the nonzero mean free path of electrons in photoresists exposed by extreme ultraviolet lithography has detrimental consequences on patterning resolution, but its effect is difficult to quantify experimentally. So far, most mean free path calculations use the dielectric formalism, which is an approximation valid in the optical limit and fails at low kinetic energy. In this work, we used a modified substrate-overlayer technique that exploited the attenuation of the Si 2p core level originating specifically from the native silicon dioxide to evaluate the attenuation of electrons traveling through 2 and 4 nm of photoresist overlayers to provide a close estimation of the inelastic mean free path relevant for photoresist lithography patterning and for electron microscopy. The photoemission spectra were collected in the proximity of the Si 2p edge (binding energy ∼101 eV) using synchrotron light of energy ℏω ranging between 120 and 550 eV. The photoresist films were prototypical chemically amplified resists based on organic copolymer of poly hydroxystyrene and tertbutyl methacrylate with and without triphenyl sulfonium perfluoro-1-butanesufonate photoacid generator and trioctylamine quencher. The inelastic mean free path of electrons, in the range that is relevant for photoresist exposure in extreme ultraviolet lithography (20-92 eV), was found to be between 1 and 2 nm. At higher kinetic energy, the mean free path increased, consistently with the well-known behavior. The presence of the photoacid generator and quencher did not change the mean free path, within experimental error. Our results are discussed and compared with the existing literature on organic molecules measured via dielectric formalism and electron transmission experiments.

The Role of Molecular Structure in Monte Carlo Simulations of the Secondary Electron Yield and Backscattering Coefficient from Methacrylic Acid.

In this paper, we show the influence of the chemical structure of four different conformers on the secondary electron emission and backscattering of an electron beam from a gel of methacrylic acid. The conformers have different permanent dipole moments, which determines the cross sections for elastic collisions with electrons. The cross sections are used in Monte Carlo simulations of an electron beam, which enters the gel of methacrylic acid. The secondary electron yield and the backscattering coefficient are computed as a function of the beam energy.

Depth Correction of 3D NanoSIMS Images Shows Intracellular Lipid and Cholesterol Distributions while Capturing the Effects of Differential Sputter Rate.

Knowledge of the distributions of drugs, metabolites, and drug carriers within cells is a prerequisite for the development of effective disease treatments. Intracellular component distribution may be imaged with high sensitivity and spatial resolution by using a NanoSIMS in the depth profiling mode. Depth correction strategies that capture the effects of differential sputtering without requiring additional measurements could enable producing accurate 3D NanoSIMS depth profiling images of intracellular component distributions. Here we describe an approach for depth correcting 3D NanoSIMS depth profiling images of cells that accounts for differential sputter rates. Our approach uses the secondary ion and secondary electron depth profiling images to reconstruct the cell's morphology at every raster plane. These cell morphology reconstructions are used to adjust the z-positions and heights of the voxels in the component-specific 3D NanoSIMS images. We validated this strategy using AFM topography data and reconstructions created from depth profiling images acquired with focused ion beam-secondary electron microscopy. Good agreement was found for the shapes and relative heights of the reconstructed morphologies. Application of this depth correction strategy to 3D NanoSIMS depth profiling images of a metabolically labeled cell better resolved the transport vesicles, organelles, and organellar membranes containing 18O-cholesterol and 15N-sphingolipids. Accurate 3D NanoSIMS images of intracellular component distributions may now be produced without requiring correlated analyses with separate instruments or the assumption of a constant sputter rate. This will allow visualization of the subcellular distributions of lipids, metabolites, drugs, and nanoparticles in 3D, information pivotal to understanding and treating disease.

Electron-beam-induced charging of an Al2O3 nanotip studied using off-axis electron holography.

Electrostatic charging of specimens during electron, photon or ion irradiation is a complicated and poorly understood phenomenon, which can affect the acquisition and interpretation of experimental data and alter the functional properties of the constituent materials. It is usually linked to secondary electron emission, but also depends on the geometry and electrical properties of the specimen. Here, we use off-axis electron holography in the transmission electron microscope to study electron-beam-induced charging of an insulating Al2O3 nanotip on a conducting support. The measurements are performed under parallel electron illumination conditions as a function of specimen temperature, electron dose, primary electron energy and surface cleanliness. We observe a lack of reproducibility of charge density measurements after cycling the specimen temperature. Surprisingly, we find both positively and negatively charged regions in closely adjacent parts of the specimen.

Contrast Mechanisms in Secondary Electron e-Beam-Induced Current (SEEBIC) Imaging.

Over the last few years, a new mode for imaging in the scanning transmission electron microscope (STEM) has gained attention as it permits the direct visualization of sample conductivity and electrical connectivity. When the electron beam (e-beam) is focused on the sample in the STEM, secondary electrons (SEs) are generated. If the sample is conductive and electrically connected to an amplifier, the SE current can be measured as a function of the e-beam position. This scenario is similar to the better-known scanning electron microscopy-based technique, electron beam-induced current imaging, except that the signal in the STEM is generated by the emission of SEs, hence the name secondary electron e-beam-induced current (SEEBIC), and in this case, the current flows in the opposite direction. Here, we provide a brief review of recent work in this area, examine the various contrast generation mechanisms associated with SEEBIC, and illustrate its use for the characterization of graphene nanoribbon devices.

Deep learning-based in vivo dose verification from proton-induced secondary-electron-bremsstrahlung images with various count level.

PURPOSE: Proton-induced secondary-electron-bremsstrahlung (SEB) imaging is a promising method for estimating the ranges of particle beam. However, SEB images do not directly represent dose distributions of particle beams. In addition, the ranges estimated from measured images were deviated because of limited spatial resolutions of the developed x-ray camera as well as statistical noise in the images. To solve these problems, we proposed a method for predicting high-resolution dose images from SEB images with various count level using a deep learning (DL) approach for range and width verification. METHODS: In this study, we adopted the double U-Net model, which is a previously proposed deep convolutional network model. The first U-Net model in the double U-Net model was used to denoise the SEB images with various count level. The first U-Net model for denoising was trained on 8000 pairs of SEB images with various count level and noise-free images which were created by a sophisticated in-house developed model function. The second U-Net model for dose prediction was trained using 8000 pairs of denoised SEB images from the first U-Net model and high-resolution dose images generated by Monte Carlo simulation. RESULTS: For both simulation and measurement data, the trained DL model could successfully predict high-resolution dose images which showed a clear Bragg peak and no statistical noise. The difference of the range and width was less than 2.1 mm, even from the SEB images measured with a decrease in the number of irradiated protons to less than 11% of 3.2 × 1011 protons. CONCLUSIONS: High-resolution dose images from measured and simulated SEB images were successfully predicted by using the trained DL model for protons. Our proposed DL model was feasible to predict dose images accurately even with smaller number of irradiated protons.

Effect of the Surface Morphology of Porous Coatings on Secondary Electron Yield of Metal Surface.

Surface roughening is an important material surface treatment technique, and it is particularly useful for use in secondary electron yield (SEY) suppression on metal surfaces. Porous structures produced via roughening on coatings have been confirmed to reduce SEY, but the regulation strategy and the influence of process parameters both remain unclear in the practical fabrication of effective porous structures. In this paper, the effect of the surface morphology of porous coatings on the SEY of aluminum alloy substrates was studied. Surface characterization and SEY measurements were carried out for samples with a specific process technique on their surfaces. An exponential fitting model of the correlation between surface roughness and the peak values of SEY curves, δm, was summarized. Furthermore, an implementation strategy to enable low surface SEY was achieved from the analysis of the effect of process parameters on surface morphology formation. This work will aid our understanding of the effect of the irregular surface morphology of porous coatings on SEY, thereby revealing low-cost access to the realization of an easy-to-scale process that enables low SEY.

Revealing Localised Mechanochemistry of Biomaterials Using In Situ Multiscale Chemical Analysis.

The study of mechanical and chemical phenomena arising within a material that is being subjected to external stress is termed mechanochemistry (MC). Recent advances in MC have revealed the prospect not only to enable a greener route to chemical transformations but also to offer previously unobtainable opportunities in the production and screening of biomaterials. To date, the field of MC has been constrained by the inability of current characterisation techniques to provide essential localised multiscale chemically mapping information. A potential method to overcome this is secondary electron hyperspectral imaging (SEHI). SEHI is a multiscale material characterisation technique applied within a scanning electron microscope (SEM). Based on the collection of secondary electron (SE) emission spectra at low primary beam energies, SEHI is applicable to the chemical assessment of uncoated polymer surfaces. Here, we demonstrate that SEHI can provide in situ MC information using poly(glycerol sebacate)-methacrylate (PGS-M) as an example biomaterial of interest. This study brings the use of a bespoke in situ SEM holder together with the application of SEHI to provide, for the first time, enhanced biomaterial mechanochemical characterisation.