Large and Pressure-Dependent c-Axis Piezoresistivity of Highly Oriented Pyrolytic Graphite near Zero Pressure.

The c-axis piezoresistivity is a fundamental and important parameter of graphite, but its value near zero pressure has not been well determined. Herein, a new method for studying the c-axis piezoresistivity of van der Waals materials near zero pressure is developed on the basis of in situ scanning electron microscopy and finite element simulation. The c-axis piezoresistivity of microscale highly oriented pyrolytic graphite (HOPG) is found to show a large value of 5.68 × 10-5 kPa-1 near zero pressure and decreases by 2 orders of magnitude to the established value of ∼10-7 kPa-1 when the pressure increases to 200 MPa. By modulating the serial tunneling barrier model on the basis of the stacking faults, we describe the c-axis electrical transport of HOPG under compression. The large c-axis piezoresistivity near zero pressure and its large decrease in magnitude with pressure are attributed to the rapid stiffening of the electromechanical properties under compression.

Stability of Plasmonic Mg-MgO Core-Shell Nanoparticles in Gas-Phase Oxidative Environments.

Magnesium is a recent addition to the plasmonic toolbox: nanomaterials that efficiently utilize photons' energy due to their ability to sustain localized surface plasmon resonances. Magnesium nanoparticles protected by a native oxide shell can efficiently absorb light across the solar spectrum, making them a promising photocatalytic material. However, their inherent reactivity toward oxidation may limit the number of reactions in which Mg-MgO can be used. Here, we investigate the stability of plasmonic Mg-MgO core-shell nanoplates under oxidative conditions. We demonstrate that the MgO shell stabilizes the metallic Mg core against oxidation in air at up to 400 °C. Furthermore, we show that the reactivity of Mg-MgO nanoplates with water vapor (3.5 vol % in N2) decreases with temperature, with no oxidation of the Mg core detected from 200 to 400 °C. This work unravels the potential of Mg-MgO nanoparticles for a broad range of catalytic transformations occurring in oxidative environments.

Chemomechanical Origins of the Dynamic Evolution of Isolated Li Filaments in Inorganic Solid-State Electrolytes.

The penetrating growth of Li into the inorganic solid-state electrolyte (SSE) is one key factor limiting its practical application. Research to understand the underlying mechanism of Li penetration has been ongoing for years and is continuing. Here, we report an in situ scanning electron microscopy methodology to investigate the dynamic behaviors of isolated Li filaments in the garnet SSE under practical cycling conditions. We find that the filaments tend to grow in the SSE, while surprisingly, those filaments can self-dissolve with a decrease in the current density without a reversal of the current direction. We further build a coupled electro-chemo-mechanical model to assess the interplay between electrochemistry and mechanics during the dynamic evolution of filaments. We reveal that filament growth is strongly regulated by the competition between the electrochemical driving force and mechanical resistive force. The numerical results provide rational guidance for the design of solid-state batteries with excellent properties.

Pull-to-Peel of Two-Dimensional Materials for the Simultaneous Determination of Elasticity and Adhesion.

The flexible and clinging nature of ultrathin films requires an understanding of their elastic and adhesive properties in a wide range of circumstances from fabrications to applications. Simultaneously measuring both properties, however, is extremely difficult as the film thickness diminishes to the nanoscale. Here we address such difficulties through peeling by pulling thin films off from the substrates (we thus refer to it as "pull-to-peel"). Particularly, we perform in situ pull-to-peel of graphene and MoS2 films in a scanning electron microscope and achieve simultaneous determination of their Young's moduli and adhesions to gold substrates. This is in striking contrast to other conceptually similar tests available in the literature, including indentation tests (only measuring elasticity) and spontaneous blisters (only measuring adhesion). Furthermore, we show a weakly nonlinear Hooke's relation for the pull-to-peel response of two-dimensional materials, which may be harnessed for the design of nanoscale force sensors or exploited in other thin-film systems.

The Limits of Electromechanical Coupling in Highly-Tensile Strained Germanium.

Speculations regarding electronic and photonic properties of strained germanium (Ge) have perpetually put it into contention for next-generation devices since the start of the information age. Here, the electromechanical coupling of <111> Ge nanowires (NWs) is reported from unstrained conditions to the ultimate tensile strength. Under tensile strain, the conductivity of the NW is enhanced exponentially, reaching an enhancement factor of ∼130 at ∼3.5% of strain. Under strains larger than ∼2.5%, the electrical properties of Ge also exhibit a dependence on the electric field. The conductivity can be further enhanced by ∼2.2× with a high bias condition at ∼3.5% of strain. Cyclic loading tests confirm that the observed electromechanical responses are repeatable, reversible, and related to the changing electronic band structure. These tests reveal the excellent prospects for utilizing strained Ge NWs in photodetector or piezoelectronic transistor applications, but significant challenges remain to realize strict direct band gap devices.

In situ liquid SEM imaging analysis revealing particle dispersity in aqueous solutions.

A quantitative description on dispersity of boehmite (γ-AlOOH) particles, a key component for waste slurry at Hanford sites, can provide useful knowledge for understanding various physicochemical nature of the waste. In situ liquid scanning electron microscopy (SEM) was used to evaluate the dispersity of particles in aqueous conditions using a microfluidic sample holder, System for Analysis at Liquid Vacuum Interface (SALVI). Secondary electron (SE) images and image analyses were performed to determine particle centroid locations and the distance to the nearest neighbour particle centroid, providing reliable rescaled interparticle distances as a function of ionic strength in acidic and basic conditions. Our finding of the particle dispersity is consistent with physical insights from corresponding particle interactions under physicochemical conditions, demonstrating delicate changes in dispersity of boehmite particles based on novel in situ liquid SEM imaging and analysis. LAY DESCRIPTION: In situ liquid scanning electron microscopy (SEM) was used to determine the interparticle distance of boehmite (γ-AlOOH) particles, a key component for waste slurry at Hanford sites. This type of quantitative measurement is important to understand various physicochemical nature of the radiological waste containing boehmite. In situ liquid SEM was enabled by a unique vacuum compatible microfluidic cell, System for Analysis at Liquid Vacuum Interface (SALVI). We collected secondary electron (SE) images and performed image analyses to determine particle centroid locations and the distance to the nearest neighbour particle centroid to arrive at the interparticle distances in acidic and basic conditions. Our results show that delicate changes occur among boehmite particles under different pH conditions using novel in situ SEM imaging.

Quantitative in Situ SEM High Cycle Fatigue: The Critical Role of Oxygen on Nanoscale-Void-Controlled Nucleation and Propagation of Small Cracks in Ni Microbeams.

This Letter presents a quantitative in situ scanning electron microscope (SEM) nanoscale high and very high cycle fatigue (HCF/VHCF) investigation of Ni microbeams under bending, using a MEMS microresonator as an integrated testing machine. The novel technique highlights ultraslow fatigue crack growth (average values down to ∼10-14 m/cycle) that has heretofore not been reported and that indicates a discontinuous process; it also reveals strong environmental effects on fatigue lives that are 3 orders of magnitude longer in a vacuum than in air. This ultraslow fatigue regime does not follow the well documented fatigue mechanisms that rely on the common crack tip stress intensification, mediated by dislocation emission and associated with much larger crack growth rates. Instead, our study reveals fatigue nucleation and propagation mechanisms that mainly result from room temperature void formation based on vacancy condensation processes that are strongly affected by oxygen. This study therefore shows significant size effects governing the bending high/very high cycle fatigue behavior of metals at the micro- and nanoscales, whereby the stress concentration effect at the tip of a growing small fatigue crack is assumed to be greatly reduced by the effect of the bending-induced extreme stress gradients, which prevents any significant cyclic crack tip opening displacement. In this scenario, ultraslow processes relying on vacancy formation at the subsurface or in the vicinity of a crack tip and subsequent condensation into voids become the dominant fatigue mechanisms.

Localized Pulsed Electrodeposition Process for Three-Dimensional Printing of Nanotwinned Metallic Nanostructures.

Nanotwinned-metals (nt-metals) offer superior mechanical (high ductility and strength) and electrical (low electromigration) properties compared to their nanocrystalline (nc) counterparts. These properties are advantageous in particular for applications in nanoscale devices. However, fabrication of nt-metals has been limited to films (two-dimensional) or template-based (one-dimensional) geometries, using various chemical and physical processes. In this Letter, we demonstrate the ambient environment localized pulsed electrodeposition process for direct printing of three-dimensional (3D) freestanding nanotwinned-Copper (nt-Cu) nanostructures. 3D nt-Cu structures were additively manufactured using pulsed electrodeposition at the tip of an electrolyte-containing nozzle. Focused ion beam (FIB) and transmission electron microscopy (TEM) analysis revealed that the printed metal was fully dense, and was mostly devoid of impurities and microstructural defects. FIB and TEM images also revealed nanocrystalline-nanotwinned-microstructure (nc-nt-microstructure), and confirmed the formation of coherent twin boundaries in the 3D-printed Cu. Mechanical properties of the 3D-printed nc-nt-Cu were characterized by direct printing (FIB-less) of micropillars for in situ SEM microcompression experiments. The 3D-printed nc-nt-Cu exhibited a flow stress of over 960 MPa, among the highest ever reported, which is remarkable for a 3D-printed material. The microstructure and mechanical properties of the nc-nt-Cu were compared to those of nc-Cu printed using the same process under direct current (DC) voltage.

In Situ Scanning Electron Microscope (SEM) Observations of Damage and Crack Growth of Shale.

To better understand the formation and evolution of hierarchical crack networks in shales, observations of microscopic damage, and crack growth were conducted using an in situ tensile apparatus inside a scanning electron microscope. An arched specimen with an artificial notch incised into the curved edge was shown to afford effective observation of the damage and crack growth process that occurs during the brittle fracturing of shale. Because this arched specimen design can induce a squeezing effect, reducing the tensile stress concentration at the crack tip, and preventing the brittle shale from unstable fracturing to some extent. Both induced and natural pores and cracks were observed at different scales around the main crack path or on fractured surfaces. Observations indicate that the crack initiation zone develops around the crack tip where tensile stresses are concentrated and micro/nanoscale cracks nucleate. Crack advancement generally occurs by the continuous generation and coalescence of damage zones having intermittent en echelon microscopic cracks located ahead of the crack tips. Mineral anisotropy and pressure build-up around crack tips causes crack kinking, deflection, and branching. Crack growth is often accompanied by the cessation or closure of former branch cracks due to elastic recovery and induced compressive stress. The branching and interactions of cracks form a three-dimensional hierarchical network that includes induced branch cracks having similar paths, as well as natural structures such as nanopores, bedding planes, and microscopic cracks.

Quantitative analysis of {332}〈113〉 twinning in a Ti-15Mo alloy by in situ scanning electron microscopy.

We have performed quantitative analysis of {332}〈113〉 twinning in a ß-Ti-15Mo (wt.%) alloy by in situ scanning electron microscopy and electron backscattering diffraction (EBSD). Microstructure-twinning relations were evaluated by statistical analysis of the evolving twin structure upon deformation at room temperature. Our analysis reveals that at the early stages of deformation (ε < 1.5 to 2.0%), primary twinning is mainly determined by the applied macroscopic stress resolved on the twin system. Most of the primary twins (~70-80% of the analyzed twins) follow Schmid's law with respect to the macroscopic stress, and most of the growth twins (~ 85% of the analyzed twins) correspond to the higher stressed variant. In the grain size range studied here (40-120 µm), we find that several twin parameters such as number of twins per grain and number of twins per grain boundary area exhibit grain size dependence. We ascribe these effects to the grain size dependence of twin nucleation stress and apparent critical resolved shear stress for twinning, respectively.

Molecular-Level Engineering of Adhesion in Carbon Nanomaterial Interfaces.

Weak interfilament van der Waals interactions are potentially a significant roadblock in the development of carbon nanotube- (CNT-) and graphene-based nanocomposites. Chemical functionalization is envisioned as a means of introducing stronger intermolecular interactions at nanoscale interfaces, which in turn could enhance composite strength. This paper reports measurements of the adhesive energy of CNT-graphite interfaces functionalized with various coverages of arylpropionic acid. Peeling experiments conducted in situ in a scanning electron microscope show significantly larger adhesive energies compared to previously obtained measurements for unfunctionalized surfaces (Roenbeck et al. ACS Nano 2014, 8 (1), 124-138). Surprisingly, however, the adhesive energies are significantly higher when both surfaces have intermediate coverages than when one surface is densely functionalized. Atomistic simulations reveal a novel functional group interdiffusion mechanism, which arises for intermediate coverages in the presence of water. This interdiffusion is not observed when one surface is densely functionalized, resulting in energy trends that correlate with those observed in experiments. This unique intermolecular interaction mechanism, revealed through the integrated experimental-computational approach presented here, provides significant insights for use in the development of next-generation nanocomposites.

New lithium metal polymer solid state battery for an ultrahigh energy: nano C-LiFePO4 versus nano Li1.2V3O8.

Novel lithium metal polymer solid state batteries with nano C-LiFePO4 and nano Li1.2V3O8 counter-electrodes (average particle size 200 nm) were studied for the first time by in situ SEM and impedance during cycling. The kinetics of Li-motion during cycling is analyzed self-consistently together with the electrochemical properties. We show that the cycling life of the nano Li1.2V3O8 is limited by the dissolution of the vanadium in the electrolyte, which explains the choice of nano C-LiFePO4 (1300 cycles at 100% DOD): with this olivine, no dissolution is observed. In combination with lithium metal, at high loading and with a stable SEI an ultrahigh energy density battery was thus newly developed in our laboratory.

Design and Application of Variable Temperature Setup for Scanning Electron Microscopy in Gases and Liquids at Ambient Conditions.

Scanning electron microscopy (SEM) of nanoscale objects in dry and fully hydrated conditions at different temperatures is of critical importance in revealing details of their interactions with an ambient environment. Currently available WETSEM capsules are equipped with thin electron-transparent membranes and allow imaging of samples at atmospheric pressure, but do not provide temperature control over the sample. Here, we developed and tested a thermoelectric cooling/heating setup for WETSEM capsules to allow ambient pressure in situ SEM studies with a temperature range between -15 and 100°C in gaseous, liquid, and frozen conditions. The design of the setup also allows for correlation of the SEM with optical microscopy and spectroscopy. As a demonstration of the possibilities of the developed approach, we performed real-time in situ microscopy studies of water condensation on a surface of Morpho sulkowskyi butterfly wing scales. We observed that initial water nucleation takes place on top of the scale ridges. These results confirmed earlier discovery of a preexisting polarity gradient of the ridges of Morpho butterflies. Our developed thermoelectric cooling/heating setup for environmental capsules meets the diverse needs for in situ nanocharacterization in material science, catalysis, microelectronics, chemistry, and biology.

Real-time dynamic behavior analysis of thin film during in-situ SEM tensile testing.

Thin films are widely used in micro/nano-electronics. To accurately evaluate the mechanical behavior of thin films, it is important to analyze their dynamic behavior during mechanical testing in real-time. However, high-magnification SEM (Scanning Electron Microscope) images for applying strain measurement require time-consuming. In this study, we propose a method for real-time dynamic behavior analysis of thin films using in-situ SEM testing and image-based strain measurement, to obtain the mechanical properties of the thin film material to ensure reliability. We developed an in-situ SEM tensile tester that can be installed within the limited space of a chamber and optimized the magnification and resolution settings to obtain images at 1 frame per second. Therefore, we applied an image-based strain measurement method as continuously acquired high-magnification images from SEM. This method enables us to analyze the dynamic behavior of thin film materials, including failure mechanism.

Microscale and Macroscale Deformation Behavior of Electrospun Polymeric Nanofiber Membranes Using In Situ SEM during Mechanical Testing.

Electrospun nanofiber membranes show high potential in various application fields (e.g., filtration, catalysis, and sensing). Nevertheless, knowledge of the mechanical behavior, and more specifically, the deformation of nanofiber membranes is still limited today which can complicate the appliance of nanofiber membranes in applications where they are mechanically loaded. In this paper, we, therefore, analyzed the mechanical behavior of polymeric nanofiber membranes with different fiber orientations (random and aligned) extensively. Polyamide 6 was used as a representative reference polymer for proof-of-concept. Mechanical tests show that all membranes have a coherent deformation behavior at the macroscale up to the point of fracture. Large variations in stiffness, ultimate strength, and ultimate strain were observed between membranes with different fiber orientations (Random: E-mod: 370 ± 34 MP; UTS: 38.5 ± 6.0 MPa; εmax: 30.0 ± 2.8%; Parallel aligned: E-mod: 753 ± 11 MPa; UTS: 55.4 ± 0.8 MPa; εmax: 12.0 ± 0.1%; Perpendicular aligned: E-mod: 24.1 ± 3.7 MPa; UTS:/; εmax: >40%). This shows the versatility and tunability of the mechanical behavior of these nanofiber membranes. At the microscale, the fibrous structure results in deformation mechanisms that resist failure formation and progression when the membrane is mechanically loaded. This results in a high fracture resistance, even for pre-damaged membranes. Realignment of the fibers along the loading direction causes crack tip blunting, locally reinforcing the membrane.

Digital Twin Modeling of Flexible Perovskite Nano-Films with In-Situ Mechanical Microscopy Validation.

Flexible perovskite solar cells introduce opportunities for high throughput, high specific weight, and short energy payback time photovoltaics. However, they require additional investigation into their mechanical resiliency. This work investigates the mechanical properties and behaviors of perovskite thin films and builds a robust model for future research. A two-pronged approach was utilized. Perovskite thin films were flexed in a three-point bend mode with in-situ SEM. Novel insights into the perovskite mechanical behaviors with varying substrate layers were gained. Modeling and validation, the second prong, was completed with finite element analysis. Model coupons of the imaged perovskite architectures were built, with sensitivity analysis completed to provide mechanical property estimates. The results demonstrate that mechanical degradation of perovskite thin films on polyethylene terephthalate (PET) primarily presents as a crack in the grain boundaries between crystals. Perovskite thin films on Indium Tin Oxide (ITO) and PET primarily crack in a periodic pattern regardless of the placement of perovskite crystals.

Realizing Holistic Charging-Discharging for Dendrite-Free Lithium Metal Anodes via Constructing Three-Dimensional Li+ Conductive Networks.

Lithium (Li) metal is a promising candidate for next-generation anode materials with high energy densities. However, Li dissolution/deposition processes are limited at the upper surface in contact with the electrolyte, which brings a locally high current density and then results in dendritic Li growth. This restraint of the local surface reaction during cycling has not been solved by commonly used modification strategies. In this study, a three-dimensional (3D) Li+ conductive skeleton is activated from atomic layer deposition (ALD) coating Li3PO4 (LPO) on the surface of the Ni foam (LPNF). Then, the skeleton is efficiently constructed in the Li metal anode by the lower-temperature Li infusion. Ionic conductor LPO layers and electronic conductor Ni fibers supply charge transport channels between the electrolyte and the internal Li. The mixed conductive network realizes holistic charge transfer, which is proved by in situ scanning electron microscopy experiments. In virtue of dispersive dissolution/deposition and optimized electrochemical kinetics brought by a Li+ conductive network, the composited Li electrode presents an excellent symmetric battery cycling stability (over 1200 h) and enhanced rate performances (stable cycling even at 10.0 mA cm-2). When matching with a LiCoO2 (LCO) cathode, LCO||Li@LPNF full batteries exhibit a capacity retention of 80.8% over 250 cycles. During cycling, there was no evidence of dendrite growth and the remaining Li in the composited anode showed a smooth, compact, and well-combined condition with LPNF. Through constructing a 3D Li+ conductive network, the composited Li metal anode breaks through the limit of the local surface reaction; this work proposes a novel insight of realizing holistic charging/discharging for the dendrite-free Li metal anode.

Investigating Iron Alloy Phase Changes Using High Temperature In Situ SEM Techniques.

This research utilises a novel heat stage combined with a Zeiss scanning electron microscope to investigate phase changes in iron alloys at temperatures up to 800 ℃ using SE and EBSD imaging. Carbon steel samples with starting structures of ferrite/pearlite were transformed into austenite using the commercial heat treatment process whilst imaging within the SEM. This process facilitates capturing both grain and phase transformation in real time allowing better insight into the microstructural evolution and overall phase change kinetics of this heat treatment. The technique for imaging uses a combination of localised EBSD high temperature imaging combined with the development of high temperature thermal-etching SE imaging technique. The SE thermal etching technique, as verified by EBSD images, enables tracking of a statistically significant number of grains (>100) and identification of individual phases. As well as being applied to carbon steel as shown here, the technique is part of a larger study on high temperature in situ SEM techniques and could be applied to a variety of alloys to study complex phase transformations.

In-situ SEM micropillar compression of porous and dense zirconia materials.

The reduction of failure rates of small-sized zirconia devices depends on the understanding of their micromechanical properties. This paper reports the micromechanical behaviors of porous and dense zirconia materials using in-situ micropillar compression with a flat diamond indenter in a scanning electron microscope (SEM). Porous and dense zirconia micropillars were made using focused ion beam (FIB) milling technique in the SEM. They were then subject to in-situ SEM compression to identify their Young's moduli, yield stresses, plastic deformation, compressive and fracture strengths, damage accumulations, and failure mechanisms. We found that while both porous and dense zirconia microstructures exhibited plastic behaviors, the former had much lower Young's moduli, strengths (yield, compression and fracture), resilience and toughness but higher ductility, resulting in significant buckling than the latter. In plastic regions, alternative strain softening and hardening may have caused stress variations in porous zirconia while dislocation movement contributed to strain hardening in dense zirconia. Although both zirconia materials had quasi-brittle failures, there were different damage mechanisms. The quasi-brittle failure for porous state was due to mushrooming buckling damage driven by breaking of weak interconnected pore networks, resulting in severe compaction and pulverization, microcracks and material piling. The quasi-brittle failure for dense state was identified as plastic crushing damage, involving microcrack initiation and propagation, cleavage and intergranular fractures, and delamination. The mechanical properties of porous and dense zirconia micropillars investigated contributed to the knowledge on deformation and damage mechanisms of zirconia materials at the small scale.

In-situ SEM cyclic nanoindentation of pre-sintered and sintered zirconia materials.

Efficient diamond machining of zirconia requires a comprehensive understanding of repetitive diamond indentation mechanics. This paper reports on in-situ cyclic nanoindentations of pre-sintered and sintered zirconia materials performed inside a scanning electron microscope (SEM). In-situ SEM imaging of cyclic indentation processes and high-magnification SEM mapping of indentation imprints were conducted. The elastic and plastic behaviors of pre-sintered and sintered zirconia materials were investigated as a function of the cyclic nanoindentation number using the Sakai and Sakai-Nowak models. For pre-sintered zirconia, cyclic nanoindentation induced quasi-plastic deformation, causing localized agglomeration of zirconia crystals with microcracks and large cracking along the indentation edge. Severely compressed, fragmented, and pulverized zirconia crystals and smeared surfaces were also observed. For sintered zirconia, shear bands dominated quasi-plastic deformation with the formation of edge pile-ups and localized microfractures occurred at indentation apex and diagonals. All elastic and plastic behaviors for pre-sintered and sintered zirconia materials revealed significantly microstructure-dependent. Pre-sintered zirconia yielded significantly lower contact hardness, Young's moduli, resistance to plasticity, elastic deformation components, and resistance to machining-induced cracking, and higher elastic and plastic displacements than sintered state. Meanwhile, all the behaviors for the two materials were independent from the cyclic nanoindentation number. A model was proposed for cyclic nanoindentation mechanics, revealing their cyclic indentation-induced microstructural changes in the two zirconia materials. This study advances the fundamental understanding of nanoindentation mechanics of zirconia materials.