In Situ Atomic-Scale Observation of 5-Fold Twin Formation in Nanoscale Crystal under Mechanical Loading.

A 5-fold twin is usually observed in nanostructured metals after mechanical tests and/or annealing treatment. However, the formation mechanism of a 5-fold twin has not been fully elaborated, due to the lack of direct time-resolved atomic-scale observation. Here, by using in situ nanomechanical testing combined with atomistic simulations, we show that sequential twinning slip in varying slip systems and decomposition of high-energy grain boundaries account for the 5-fold twin formation in a nanoscale gold single crystal under bending as well as the reversible formation and dissolution of a 5-fold twin in a nanocrystal with a preexisting twin under tension and shearing. Moreover, we find that the complex stress state in the neck area results in the breakdown of Schmid's law, causing 5-fold twin formation in a gold nanocrystal with a twin boundary parallel to the loading direction. These findings enrich our understanding of the formation process of high-order twin structures in nanostructured metals.

Atomistic observation on diffusion-mediated friction between single-asperity contacts.

The field of nanotribology has long suffered from the inability to directly observe what takes place at a sliding interface. Although techniques based on atomic force microscopy have identified many friction phenomena at the nanoscale, many interpretative pitfalls still result from the indirect or ex situ characterization of contacting surfaces. Here we combined in situ high-resolution transmission electron microscopy and atomic force microscopy measurements to provide direct real-time observations of atomic-scale interfacial structure during frictional processes and discovered the formation of a loosely packed interfacial layer between two metallic asperities that enabled a low friction under tensile stress. This finding is corroborated by molecular dynamic simulations. The loosely packed interfacial layer became an ordered layer at equilibrium distances under compressive stress, which led to a transition from a low-friction to a dissipative high-friction motion. This work directly unveils a unique role of atomic diffusion in the friction of metallic contacts.

Size-dependent dynamic structures of supported gold nanoparticles in CO oxidation reaction condition.

Gold (Au) catalysts exhibit a significant size effect, but its origin has been puzzling for a long time. It is generally believed that supported Au clusters are more or less rigid in working condition, which inevitably leads to the general speculation that the active sites are immobile. Here, by using atomic resolution in situ environmental transmission electron microscopy, we report size-dependent structure dynamics of single Au nanoparticles on ceria (CeO2) in CO oxidation reaction condition at room temperature. While large Au nanoparticles remain rigid in the catalytic working condition, ultrasmall Au clusters lose their intrinsic structures and become disordered, featuring vigorous structural rearrangements and formation of dynamic low-coordinated atoms on surface. Ab initio molecular-dynamics simulations reveal that the interaction between ultrasmall Au cluster and CO molecules leads to the dynamic structural responses, demonstrating that the shape of the catalytic particle under the working condition may totally differ from the shape under the static condition. The present observation provides insight on the origin of superior catalytic properties of ultrasmall gold clusters.

Formation of monatomic metallic glasses through ultrafast liquid quenching.

It has long been conjectured that any metallic liquid can be vitrified into a glassy state provided that the cooling rate is sufficiently high. Experimentally, however, vitrification of single-element metallic liquids is notoriously difficult. True laboratory demonstration of the formation of monatomic metallic glass has been lacking. Here we report an experimental approach to the vitrification of monatomic metallic liquids by achieving an unprecedentedly high liquid-quenching rate of 10(14) K s(-1). Under such a high cooling rate, melts of pure refractory body-centred cubic (bcc) metals, such as liquid tantalum and vanadium, are successfully vitrified to form metallic glasses suitable for property interrogations. Combining in situ transmission electron microscopy observation and atoms-to-continuum modelling, we investigated the formation condition and thermal stability of the monatomic metallic glasses as obtained. The availability of monatomic metallic glasses, being the simplest glass formers, offers unique possibilities for studying the structure and property relationships of glasses. Our technique also shows great control over the reversible vitrification-crystallization processes, suggesting its potential in micro-electromechanical applications. The ultrahigh cooling rate, approaching the highest liquid-quenching rate attainable in the experiment, makes it possible to explore the fast kinetics and structural behaviour of supercooled metallic liquids within the nanosecond to picosecond regimes.

Slip-activated surface creep with room-temperature super-elongation in metallic nanocrystals.

Nanoscale metallic crystals have been shown to follow a 'smaller is stronger' trend. However, they usually suffer from low ductility due to premature plastic instability by source-limited crystal slip. Here, by performing in situ atomic-scale transmission electron microscopy, we report unusual room-temperature super-elongation without softening in face-centred-cubic silver nanocrystals, where crystal slip serves as a stimulus to surface diffusional creep. This interplay mechanism is shown experimentally and theoretically to govern the plastic deformation of nanocrystals over a material-dependent sample diameter range between the lower and upper limits for nanocrystal stability by surface diffusional creep and dislocation plasticity, respectively, which extends far beyond the maximum size for pure diffusion-mediated deformation (for example, Coble-type creep). This work provides insight into the atomic-scale coupled diffusive-displacive deformation mechanisms, maximizing ductility and strength simultaneously in nanoscale materials.

High-Performance Rh2P Electrocatalyst for Efficient Water Splitting.

The search for active, stable, and cost-efficient electrocatalysts for hydrogen production via water splitting could make a substantial impact on energy technologies that do not rely on fossil fuels. Here we report the synthesis of rhodium phosphide electrocatalyst with low metal loading in the form of nanocubes (NCs) dispersed in high-surface-area carbon (Rh2P/C) by a facile solvo-thermal approach. The Rh2P/C NCs exhibit remarkable performance for hydrogen evolution reaction and oxygen evolution reaction compared to Rh/C and Pt/C catalysts. The atomic structure of the Rh2P NCs was directly observed by annular dark-field scanning transmission electron microscopy, which revealed a phosphorus-rich outermost atomic layer. Combined experimental and computational studies suggest that surface phosphorus plays a crucial role in determining the robust catalyst properties.

Tuning the Outward to Inward Swelling in Lithiated Silicon Nanotubes via Surface Oxide Coating.

Electrochemically induced mechanical degradation hinders the application of Si anodes in advanced lithium-ion batteries. Hollow structures and surface coatings have been often used to mitigate the degradation of Si-based anodes. However, the structural change and degradation mechanism during lithiation/delithiation of hollow Si structures with coatings remain unclear. Here, we combine in situ TEM experiment and chemomechanical modeling to study the electrochemically induced swelling of amorphous-Si (a-Si) nanotubes with different thicknesses of surface SiOx layers. Surprisingly, we find that no inward expansion occurs at the inner surface during lithiation of a-Si nanotubes with native oxides. In contrast, inward expansion can be induced by increasing the thickness of SiOx on the outer surface, thus reducing the overall outward swelling of the lithiated nanotube. Moreover, both the sandwich lithiation mechanism and the two-stage lithiation process in a-Si nanotubes remain unchanged with the increasing thickness of surface coatings. Our chemomechanical modeling reveals the mechanical confinement effects in lithiated a-Si nanotubes with and without SiOx coatings. This work not only provides insights into the degradation of nanotube anodes with surface coatings but also sheds light onto the optimal design of hollow anodes for high-performance lithium-ion batteries.

In Situ Observation on Dislocation-Controlled Sublimation of Mg Nanoparticles.

Sublimation is an important endothermic phase transition in which the atoms break away from their neighbors in the crystal lattice and are removed into the gas phase. Such debonding process may be significantly influenced by dislocations, the crystal defect that changes the bonding environment of local atoms. By performing systematic defects characterization and in situ transmission electron microscopy (TEM) tests on a core--shell MgO-Mg system, which enables us to "modulate" the internal dislocation density, we investigated the role of dislocations on materials' sublimation with particular focus on the sublimation kinetics and mechanism. It was observed that the sublimation rate increases significantly with dislocation density. As the density of screw dislocations is high, the intersection of screw dislocation spirals creates a large number of monatomic ledges, resulting in a "liquid-like" motion of solid-gas interface, which significantly deviates from the theoretically predicted sublimation plane. Our calculation based on density functional theory demonstrated that the remarkable change of sublimation rate with dislocation density is due to the dramatic reduction in binding energy of the monatomic ledges. This study provides direct observation to improve our understanding on this fundamental phase transition as well as to shed light on tuning materials' sublimation by "engineering" dislocation density in applications.

Size-Dependent Brittle-to-Ductile Transition in Silica Glass Nanofibers.

Silica (SiO2) glass, an essential material in human civilization, possesses excellent formability near its glass-transition temperature (Tg > 1100 °C). However, bulk SiO2 glass is very brittle at room temperature. Here we show a surprising brittle-to-ductile transition of SiO2 glass nanofibers at room temperature as its diameter reduces below 18 nm, accompanied by ultrahigh fracture strength. Large tensile plastic elongation up to 18% can be achieved at low strain rate. The unexpected ductility is due to a free surface affected zone in the nanofibers, with enhanced ionic mobility compared to the bulk that improves ductility by producing more bond-switching events per irreversible bond loss under tensile stress. Our discovery is fundamentally important for understanding the damage tolerance of small-scale amorphous structures.

In situ atomic-scale observation of twinning-dominated deformation in nanoscale body-centred cubic tungsten.

Twinning is a fundamental deformation mode that competes against dislocation slip in crystalline solids. In metallic nanostructures, plastic deformation requires higher stresses than those needed in their bulk counterparts, resulting in the 'smaller is stronger' phenomenon. Such high stresses are thought to favour twinning over dislocation slip. Deformation twinning has been well documented in face-centred cubic (FCC) nanoscale crystals. However, it remains unexplored in body-centred cubic (BCC) nanoscale crystals. Here, by using in situ high-resolution transmission electron microscopy and atomistic simulations, we show that twinning is the dominant deformation mechanism in nanoscale crystals of BCC tungsten. Such deformation twinning is pseudoelastic, manifested through reversible detwinning during unloading. We find that the competition between twinning and dislocation slip can be mediated by loading orientation, which is attributed to the competing nucleation mechanism of defects in nanoscale BCC crystals. Our work provides direct observations of deformation twinning as well as new insights into the deformation mechanism in BCC nanostructures.

Strong Hall-Petch Type Behavior in the Elastic Strain Limit of Nanotwinned Gold Nanowires.

Pushing the limits of elastic deformation in nanowires subjected to stress is important for the design and performance of nanoscale devices from elastic strain engineering. Particularly, introducing nanoscale twins has proved effective in rising the tensile strength of metals. However, attaining ideal elastic strains in nanotwinned materials remains challenging, because nonuniform twin sizes locally affect the yielding behavior. Here, using in situ high-resolution transmission electron microscopy tensile testing of nanotwinned [111]-oriented gold nanowires, we report direct lattice-strain measurements that demonstrate a strong Hall-Petch type relationship in the elastic strain limit up to 5.3%, or near the ideal theoretical limit, as the twin size is decreased below 3 nm. It is found that the largest twin in nanowires with irregular twin sizes controls the slip nucleation and yielding processes in pure tension, which is in agreement with earlier atomistic simulations. Continuous hardening behavior without loss of strength or softening is observed in nanotwinned single-crystalline gold nanowires, which differs from the behaviors of bulk nanocrystalline and nanotwinned-nanocrystalline metals. These findings are of practical value for the use of nanotwinned metallic and semiconductor nanowires in strain-engineered functional microdevices.

Atomistic Conversion Reaction Mechanism of WO3 in Secondary Ion Batteries of Li, Na, and Ca.

Intercalation and conversion are two fundamental chemical processes for battery materials in response to ion insertion. The interplay between these two chemical processes has never been directly seen and understood at atomic scale. Here, using in situ HRTEM, we captured the atomistic conversion reaction processes during Li, Na, Ca insertion into a WO3 single crystal model electrode. An intercalation step prior to conversion is explicitly revealed at atomic scale for the first time for Li, Na, Ca. Nanoscale diffraction and ab initio molecular dynamic simulations revealed that after intercalation, the inserted ion-oxygen bond formation destabilizes the transition-metal framework which gradually shrinks, distorts and finally collapses to an amorphous W and Mx O (M=Li, Na, Ca) composite structure. This study provides a full atomistic picture of the transition from intercalation to conversion, which is of essential importance for both secondary ion batteries and electrochromic devices.

Liquid-like pseudoelasticity of sub-10-nm crystalline silver particles.

In nanotechnology, small-volume metals with large surface area are used as electrodes, catalysts, interconnects and antennae. Their shape stability at room temperature has, however, been questioned. Using in situ high-resolution transmission electron microscopy, we find that Ag nanoparticles can be deformed like a liquid droplet but remain highly crystalline in the interior, with no sign of dislocation activity during deformation. Surface-diffusion-mediated pseudoelastic deformation is evident at room temperature, which can be driven by either an external force or capillary-energy minimization. Atomistic simulations confirm that such highly unusual Coble pseudoelasticity can indeed happen for sub-10-nm Ag particles at room temperature and at timescales from seconds to months.

Atomic resolution observation of conversion-type anode RuO2 during the first electrochemical lithiation.

Transition metal oxides have attracted great interest as alternative anode materials for rechargeable lithium-ion batteries. Among them, ruthenium dioxide is considered to be a prototype material that reacts with the Li ions in the conversion type. In situ transmission electron microscopy reveals a two-step process during the initial lithiation of the RuO2 nanowire anode at atomic resolution. The first step is characterized by the formation of the intermediate phase LixRuO2 due to the Li-ion intercalation. The following step is manifested by the solid-state amorphization reaction driven by advancing the reaction front. The crystalline/amorphous interface is consisted of {011} atomic terraces, revealing the orientation-dependent mobility. In the crystalline matrix, lattice disturbance and dislocation are identified to be two major stress-induced distortions. The latter can be effective diffusion channels, facilitating transportation of the Li ions inside the bulk RuO2 crystal and further resulting in non-uniform Li-ion distribution. It is expected that the local enrichment of the Li ions may account for the homogeneous nucleation of dislocations in the bulk RuO2 crystal and the special island-like structures. These results elucidate the structural evolution and the phase transformation during electrochemical cycling, which sheds light on engineering RuO2 anode materials.

Dynamic process of phase transition from wurtzite to zinc blende structure in InAs nanowires.

In situ high-resolution transmission electron microscopy revealed the precipitation of the zinc-blende (ZB) structure InAs at the liquid/solid interface or liquid/solid/amorphous carbon triple point at high temperature. Subsequent to its precipitation, detailed analysis demonstrates unique solid to solid wurtzite (WZ) to ZB phase transition through gliding of sharp steps with Shockley partial dislocations. The most intriguing phenomenon was that each step is 6 {111} atomic layers high and the step migrated without any mechanical stress applied. We believe that this is the first direct in situ observation of WZ-ZB transition in semiconductor nanowires. A model was proposed in which three Shockley partial dislocations collectively glide on every two {0001} planes (corresponds to six atomic planes in an unit). The collective glide mechanism does not need any applied shear stress.

In situ transmission electron microscopy observations of electrochemical oxidation of Li2O2.

In this Letter, we report the first in situ transmission electron microscopy observation of electrochemical oxidation of Li2O2, providing insights into the rate limiting processes that govern charge in Li-O2 cells. In these studies, oxidation of electrochemically formed Li2O2 particles, supported on multiwall carbon nanotutubes (MWCNTs), was found to occur preferentially at the MWCNT/Li2O2 interface, suggesting that electron transport in Li2O2 ultimately limits the oxidation kinetics at high rates or overpotentials.

Two-phase electrochemical lithiation in amorphous silicon.

Lithium-ion batteries have revolutionized portable electronics and will be a key to electrifying transport vehicles and delivering renewable electricity. Amorphous silicon (a-Si) is being intensively studied as a high-capacity anode material for next-generation lithium-ion batteries. Its lithiation has been widely thought to occur through a single-phase mechanism with gentle Li profiles, thus offering a significant potential for mitigating pulverization and capacity fade. Here, we discover a surprising two-phase process of electrochemical lithiation in a-Si by using in situ transmission electron microscopy. The lithiation occurs by the movement of a sharp phase boundary between the a-Si reactant and an amorphous Li(x)Si (a-Li(x)Si, x ~ 2.5) product. Such a striking amorphous-amorphous interface exists until the remaining a-Si is consumed. Then a second step of lithiation sets in without a visible interface, resulting in the final product of a-Li(x)Si (x ~ 3.75). We show that the two-phase lithiation can be the fundamental mechanism underpinning the anomalous morphological change of microfabricated a-Si electrodes, i.e., from a disk shape to a dome shape. Our results represent a significant step toward the understanding of the electrochemically driven reaction and degradation in amorphous materials, which is critical to the development of microstructurally stable electrodes for high-performance lithium-ion batteries.

In situ observation of the atomic shuffles during the { 11 2 ¯ 1 } twinning in hexagonal close-packed rhenium.

Twinning, on par with dislocations, is critically required in plastic deformation of hexagonal close-packed crystals at low temperatures. In contrast to that in cubic-structured crystals, twinning in hexagonal close-packed crystals requires atomic shuffles in addition to shear. Though the twinning shear that is carried by twinning dislocations has been captured for decades, direct experimental observation of the atomic shuffles, especially when the shuffling mode is not unique and does not confine to the plane of shear, remains a formidable challenge to date. Here, by using in-situ transmission electron microscopy, we directly capture the atomic mechanism of the 11 2 ¯ 1 twinning in hexagonal close packed rhenium nanocrystals. Results show that the 11 2 ¯ 1 twinning is dominated by the (b1/2, h1/2) twinning disconnections. In contrast to conventional expectations, the atomic shuffles accompanying the twinning disconnections proceed on alternative basal planes along 1/6 1 1 ¯ 00 , which may be attributed to the free surface in nanocrystal samples, leading to a lack of mirror symmetry across the 11 2 ¯ 1 twin boundary.

Atomic-scale observation of nucleation- and growth-controlled deformation twinning in body-centered cubic nanocrystals.

Twinning is an essential mode of plastic deformation for achieving superior strength and ductility in metallic nanostructures. It has been generally believed that twinning-induced plasticity in body-centered cubic (BCC) metals is controlled by twin nucleation, but facilitated by rapid twin growth once the nucleation energy barrier is overcome. By performing in situ atomic-scale transmission electron microscopy straining experiments and atomistic simulations, we find that deformation twinning in BCC Ta nanocrystals larger than 15 nm in diameter proceeds by reluctant twin growth, resulting from slow advancement of twinning partials along the boundaries of finite-sized twin structures. In contrast, reluctant twin growth can be obviated by reducing the nanocrystal diameter to below 15 nm. As a result, the nucleated twin structure penetrates quickly through the cross section of nanocrystals, enabling fast twin growth via facile migration of twin boundaries leading to large uniform plastic deformation. The present work reveals a size-dependent transition in the nucleation- and growth-controlled twinning mechanism in BCC metals, and provides insights for exploiting twinning-induced plasticity and breaking strength-ductility limits in nanostructured BCC metals.

Microstructural evolution of tin nanoparticles during in situ sodium insertion and extraction.

The microstructural changes and phase transformations of tin nanoparticles during electrochemical sodiation were studied with a nanosized sodium ion battery using in situ transmission electron microscopy. It was found that the first sodiation process occurred in two steps; that is, the crystalline Sn nanoparticles were initially sodiated via a two-phase mechanism with a migrating phase boundary to form a Na-poor, amorphous Na(x)Sn alloy (x ~ 0.5), which was further sodiated to several Na-rich amorphous phases and finally to the crystallized Na(15)Sn(4) (x = 3.75) via a single-phase mechanism. The volumetric expansion was about 60% in the first step and 420% after the second step. However, despite the huge expansion, cracking or fracture was not observed, which is attributed to the second step of the single-phase sodiation that accommodates large portion of the sodiation-induced stress over the entire particle. Excellent cyclability was also observed during the reversible sodiation/desodiation cycles, showing great potential of Sn nanoparticles as a robust electrode material for rechargeable batteries.