Observing growth and interfacial dynamics of nanocrystalline ice in thin amorphous ice films.

Ice crystals at low temperatures exhibit structural polymorphs including hexagonal ice, cubic ice, or a hetero-crystalline mixture of the two phases. Despite the significant implications of structure-dependent roles of ice, mechanisms behind the growths of each polymorph have been difficult to access quantitatively. Using in-situ cryo-electron microscopy and computational ice-dynamics simulations, we directly observe crystalline ice growth in an amorphous ice film of nanoscale thickness, which exhibits three-dimensional ice nucleation and subsequent two-dimensional ice growth. We reveal that nanoscale ice crystals exhibit polymorph-dependent growth kinetics, while hetero-crystalline ice exhibits anisotropic growth, with accelerated growth occurring at the prismatic planes. Fast-growing facets are associated with low-density interfaces that possess higher surface energy, driving tetrahedral ordering of interfacial H2O molecules and accelerating ice growth. These findings, based on nanoscale observations, improve our understanding on early stages of ice formation and mechanistic roles of the ice interface.

Antibacterial PLA/Mg composite with enhanced mechanical and biological performance for biodegradable orthopedic implants.

Biodegradability, bone-healing rate, and prevention of bacterial infection are critical factors for orthopedic implants. Polylactic acid (PLA) is a good candidate biodegradable material; however, it has insufficient mechanical strength and bioactivity for orthopedic implants. Magnesium (Mg), has good bioactivity, biodegradability, and sufficient mechanical properties, similar to that of bone. Moreover, Mg has an inherent antibacterial property via a photothermal effect, which generates localized heat, thus preventing bacterial infection. Therefore, Mg is a good candidate material for PLA composites, to improve their mechanical and biological performance and add an antibacterial property. Herein, we fabricated an antibacterial PLA/Mg composite for enhanced mechanical and biological performance with an antibacterial property for application as biodegradable orthopedic implants. The composite was fabricated with 15 and 30 vol% of Mg homogeneously dispersed in PLA without the generation of a defect using a high-shear mixer. The composites exhibited an enhanced compressive strength of 107.3 and 93.2 MPa, and stiffness of 2.3 and 2.5 GPa, respectively, compared with those of pure PLA which were 68.8 MPa and 1.6 GPa, respectively. Moreover, the PLA/Mg composite at 15 vol% Mg exhibited significant improvement of biological performance in terms of enhanced initial cell attachment and cell proliferation, whereas the composite at 30 vol% Mg showed deteriorated cell proliferation and differentiation because of the rapid degradation of the Mg particles. In turn, the PLA/Mg composites exerted an antibacterial effect based on the inherent antibacterial property of Mg as well as the photothermal effect induced by near-infrared (NIR) treatment, which can minimize infection after implantation surgery. Therefore, antibacterial PLA/Mg composites with enhanced mechanical and biological performance may be a candidate material with great potential for biodegradable orthopedic implants.

Shape Transformation Mechanism of Gold Nanoplates.

Shape control is of key importance in utilizing the structure-property relationship of nanocrystals. The high surface-to-volume ratio of nanocrystals induces dynamic surface reactions on exposed facets of nanocrystals, such as adsorption, desorption, and diffusion of surface atoms, all of which are important in overall shape transformation. However, it is difficult to track shape transformation of nanocrystals and understand the underlying mechanism at the level of distinguishing events on individual facets. Herein, we investigate changes of individual surface-exposed facets during diverse shape transformations of Au nanocrystals using liquid phase TEM in various chemical potentials and kinetic Monte Carlo simulations. The results reveal that the diffusion of surface atoms on nanocrystals is the governing factor in determining the final structure in shape transformation, causing the fast transformation of unstable facets to truncated morphology with minimized surface energy. The role of surface diffusion introduced here can be further applied to understanding the formation mechanism of variously shaped nanocrystals.

Observation of H2 Evolution and Electrolyte Diffusion on MoS2 Monolayer by In Situ Liquid-Phase Transmission Electron Microscopy.

Unit-cell-thick MoS2 is a promising electrocatalyst for the hydrogen evolution reaction (HER) owing to its tunable catalytic activity, which is determined based on the energetics and molecular interactions of different types of HER active sites. Kinetic responses of MoS2 active sites, including the reaction onset, diffusion of the electrolyte and H2 bubbles, and continuation of these processes, are important factors affecting the catalytic activity of MoS2 . Investigating these factors requires a direct real-time analysis of the HER occurring on spatially independent active sites. Herein, the H2 evolution and electrolyte diffusion on the surface of MoS2 are observed in real time by in situ electrochemical liquid-phase transmission electron microscopy (LPTEM). Time-dependent LPTEM observations reveal that different types of active sites are sequentially activated under the same conditions. Furthermore, the electrolyte flow to these sites is influenced by the reduction potential and site geometry, which affects the bubble detachment and overall HER activity of MoS2 .

Coalescence dynamics of platinum group metal nanoparticles revealed by liquid-phase transmission electron microscopy.

Coalescence, one of the major pathways observed in the growth of nanoparticles, affects the structural diversity of the synthesized nanoparticles in terms of sizes, shapes, and grain boundaries. As coalescence events occur transiently during the growth of nanoparticles and are associated with the interaction between nanoparticles, mechanistic understanding is challenging. The ideal platform to study coalescence events may require real-time tracking of nanoparticle growth trajectories with quantitative analysis for coalescence events. Herein, we track nanoparticle growth trajectories using liquid-cell transmission electron microscopy (LTEM) to investigate the role of coalescence in nanoparticle formation and their morphologies. By evaluating multiple coalescence events for different platinum group metals, we reveal that the surface energy and ligand binding energy determines the rate of the reshaping process and the resulting final morphology of coalesced nanoparticles. The coalescence mechanism, based on direct LTEM observation explains the structures of noble metal nanoparticles that emerge in colloidal synthesis.

Liquid-Phase Transmission Electron Microscopy for Reliable In Situ Imaging of Nanomaterials.

Liquid-phase transmission electron microscopy (LPTEM) is a powerful in situ visualization technique for directly characterizing nanomaterials in the liquid state. Despite its successful application in many fields, several challenges remain in achieving more accurate and reliable observations. We present LPTEM in chemical and biological applications, including studies for the morphological transformation and dynamics of nanoparticles, battery systems, catalysis, biomolecules, and organic systems. We describe the possible interactions and effects of the electron beam on specimens during observation and present sample-specific approaches to mitigate and control these electron-beam effects. We provide recent advances in achieving atomic-level resolution for liquid-phase investigation of structures anddynamics. Moreover, we discuss the development of liquid cell platforms and the introduction of machine-learning data processing for quantitative and objective LPTEM analysis.

Conformation Dynamics of Single Polymer Strands in Solution.

Conformational changes in macromolecules significantly affect their functions and assembly into high-level structures. Despite advances in theoretical and experimental studies, investigations into the intrinsic conformational variations and dynamic motions of single macromolecules remain challenging. Here, liquid-phase transmission electron microscopy enables the real-time tracking of single-chain polymers. Imaging linear polymers, synthetically dendronized with conjugated aromatic groups, in organic solvent confined within graphene liquid cells, directly exhibits chain-resolved conformational dynamics of individual semiflexible polymers. These experimental and theoretical analyses reveal that the dynamic conformational transitions of the single-chain polymer originate from the degree of intrachain interactions. In situ observations also show that such dynamics of the single-chain polymer are significantly affected by environmental factors, including surfaces and interfaces.

Metastable hexagonal close-packed palladium hydride in liquid cell TEM.

Metastable phases-kinetically favoured structures-are ubiquitous in nature1,2. Rather than forming thermodynamically stable ground-state structures, crystals grown from high-energy precursors often initially adopt metastable structures depending on the initial conditions, such as temperature, pressure or crystal size1,3,4. As the crystals grow further, they typically undergo a series of transformations from metastable phases to lower-energy and ultimately energetically stable phases1,3,4. Metastable phases sometimes exhibit superior physicochemical properties and, hence, the discovery and synthesis of new metastable phases are promising avenues for innovations in materials science1,5. However, the search for metastable materials has mainly been heuristic, performed on the basis of experiences, intuition or even speculative predictions, namely 'rules of thumb'. This limitation necessitates the advent of a new paradigm to discover new metastable phases based on rational design. Such a design rule is embodied in the discovery of a metastable hexagonal close-packed (hcp) palladium hydride (PdHx) synthesized in a liquid cell transmission electron microscope. The metastable hcp structure is stabilized through a unique interplay between the precursor concentrations in the solution: a sufficient supply of hydrogen (H) favours the hcp structure on the subnanometre scale, and an insufficient supply of Pd inhibits further growth and subsequent transition towards the thermodynamically stable face-centred cubic structure. These findings provide thermodynamic insights into metastability engineering strategies that can be deployed to discover new metastable phases.

In Situ Liquid Phase TEM of Nanoparticle Formation and Diffusion in a Phase-Separated Medium.

Colloidal nanoparticles are synthesized in a complex reaction mixture that has an inhomogeneous chemical environment induced by local phase separation of the medium. Nanoparticle syntheses based on micelles, emulsions, flow of different fluids, injection of ionic precursors in organic solvents, and mixing the metal organic phase of precursors with an aqueous phase of reducing agents are well established. However, the formation mechanism of nanoparticles in the phase-separated medium is not well understood because of the complexity originating from the presence of phase boundaries as well as nonuniform chemical species, concentrations, and viscosity in different phases. Herein, we investigate the formation mechanism and diffusion of silver nanoparticles in a phase-separated medium by using liquid phase transmission electron microscopy and many-body dissipative particle dynamics simulations. A quantitative analysis of the individual growth trajectories reveals that a large portion of silver nanoparticles nucleate and grow rapidly at the phase boundaries, where metal ion precursors and reducing agents from the two separated phases react to form monomers. The results suggest that the motion of the silver nanoparticles at the interfaces is highly affected by the interaction with polymers and exhibits superdiffusive dynamics because of the polymer relaxation.

Real-space imaging of nanoparticle transport and interaction dynamics by graphene liquid cell TEM.

Thermal motion of colloidal nanoparticles and their cohesive interactions are of fundamental importance in nanoscience but are difficult to access quantitatively, primarily due to the lack of the appropriate analytical tools to investigate the dynamics of individual particles at nanoscales. Here, we directly monitor the stochastic thermal motion and coalescence dynamics of gold nanoparticles smaller than 5 nm, using graphene liquid cell (GLC) transmission electron microscopy (TEM). We also present a novel model of nanoparticle dynamics, providing a unified, quantitative explanation of our experimental observations. The nanoparticles in a GLC exhibit non-Gaussian, diffusive motion, signifying dynamic fluctuation of the diffusion coefficient due to the dynamically heterogeneous environment surrounding nanoparticles, including organic ligands on the nanoparticle surface. Our study shows that the dynamics of nanoparticle coalescence is controlled by two elementary processes: diffusion-limited encounter complex formation and the subsequent coalescence of the encounter complex through rotational motion, where surface-passivating ligands play a critical role.

Wafer-Scale Production of Transition Metal Dichalcogenides and Alloy Monolayers by Nanocrystal Conversion for Large-Scale Ultrathin Flexible Electronics.

Two-dimensional (2D) transition metal dichalcogenide (TMD) layers are unit-cell thick materials with tunable physical properties according to their size, morphology, and chemical composition. Their transition of lab-scale research to industrial-scale applications requires process development for the wafer-scale growth and scalable device fabrication. Herein, we report on a new type of atmospheric pressure chemical vapor deposition (APCVD) process that utilizes colloidal nanoparticles as process-scalable precursors for the wafer-scale production of TMD monolayers. Facile uniform distribution of nanoparticle precursors on the entire substrate leads to the wafer-scale uniform synthesis of TMD monolayers with the controlled size and morphology. Composition-controlled TMD alloy monolayers with tunable bandgaps can be produced by simply mixing dual nanoparticle precursor solutions in the desired ratio. We also demonstrate the fabrication of ultrathin field-effect transistors and flexible electronics with uniformly controlled performance by using TMD monolayers.

Ligand-Dependent Coalescence Behaviors of Gold Nanoparticles Studied by Multichamber Graphene Liquid Cell Transmission Electron Microscopy.

The formation mechanism of colloidal nanoparticles is complex because significant nonclassical pathways coexist with the conventional nucleation and growth processes. Particularly, the coalescence of the growing clusters determines the final morphology and crystallinity of the synthesized nanoparticles. However, the experimental investigation of the coalescence mechanism is a challenge because the process is highly kinetic and correlates with surface ligands that dynamically modify the surface energy and the interparticle interactions of nanoparticles. Here, we employ quantitative in situ TEM with multichamber graphene liquid cell to observe the coalescence processes occurring in the synthesis of gold nanoparticles in different ligand systems, thus affording us an insight into their ligand-dependent coalescence kinetics. The analyses of numerous liquid-phase TEM trajectories of the coalescence and MD simulations of the ligand shells demonstrate that enhanced ligand mobility, employing a heterogeneous ligand mixture, results in the rapid nanoparticle pairing approach and a fast post-merging structural relaxation.

A Large-Scale Array of Ordered Graphene-Sandwiched Chambers for Quantitative Liquid-Phase Transmission Electron Microscopy.

Liquid-phase transmission electron microscopy (TEM) offers a real-time microscopic observation of the nanometer scale for understanding the underlying mechanisms of the growth, etching, and interactions of colloidal nanoparticles. Despite such unique capability and potential application in diverse fields of analytical chemistry, liquid-phase TEM studies rely on information obtained from the limited number of observed events. In this work, a novel liquid cell with a large-scale array of highly ordered nanochambers is constructed by sandwiching an anodic aluminum oxide membrane between graphene sheets. TEM analysis of colloidal gold nanoparticles dispersed in the liquid is conducted, employing the fabricated nanochamber array, to demonstrate the potential of the nanochamber array in quantitative liquid-phase TEM. The independent TEM observations in the multiple nanochambers confirm that the monomer attachment and coalescence processes universally govern the overall growth of nanoparticles, although individual nanoparticles follow different growth trajectories.

Unraveling the mystery of ultrafine bubbles: Establishment of thermodynamic equilibrium for sub-micron bubbles and its implications.

HYPOTHESIS: We test the validity of the Young-Laplace equation and Henry's law for sub-micron bubble suspensions, which has long been a questionable issue. Application of the two theories allows characterization of bubble diameter and gas molecule partitioning between gaseous and dissolved phases using two easily measurable variables: total gas content (CT) and bubble volume concentration (BVC). EXPERIMENTS: We measure CT and BVC for sub-micron bubble suspensions generated from three pure gases, which allows calculation of bubble diameter for each suspension using the Young-Laplace equation and Henry's law. Uncertainties involved in the experimental measurements are assessed. Bubble size for each suspension is also directly measured using a dynamic light scattering (DLS) technique for comparison. FINDINGS: Applying the two theories we calculate that the bubble diameters are in the range of 304-518 nm, which correspond very well with the DLS-measured diameters. Sensitivity analyses demonstrate that the correspondence of the calculated and DLS-measured bubble diameters should take place only if the two theories are valid. The gas molecule partitioning analysis shows that >96% of gas molecules in the suspension exist as dissolved phase, which suggests the significance of the dissolved phase for applications of the bubble suspensions.

Redox-Sensitive Facet Dependency in Etching of Ceria Nanocrystals Directly Observed by Liquid Cell TEM.

Defining the redox activity of different surface facets of ceria nanocrystals is important for designing an efficient catalyst. Especially in liquid-phase reactions, where surface interactions are complicated, direct investigation in a native environment is required to understand the facet-dependent redox properties. Using liquid cell TEM, we herein observed the etching of ceria-based nanocrystals under the control of redox-governing factors. Direct nanoscale observation reveals facet-dependent etching kinetics, thus identifying the specific facet ({100} for reduction and {111} for oxidation) that governs the overall etching under different chemical conditions. Under each redox condition, the contribution of the predominant facet increases as the etching reactivity increases.

Amorphous-Phase-Mediated Crystallization of Ni Nanocrystals Revealed by High-Resolution Liquid-Phase Electron Microscopy.

Nonclassical features of crystallization in solution have been recently identified both experimentally and theoretically. In particular, an amorphous-phase-mediated pathway is found in various crystallization systems as an important route, different from the classical nucleation and growth model. Here, we utilize high-resolution in situ transmission electron microscopy with graphene liquid cells to study amorphous-phase-mediated formation of Ni nanocrystals. An amorphous phase is precipitated in the initial stage of the reaction. Within the amorphous particles, crystalline domains nucleate and eventually form nanocrystals. In addition, unique crystallization behaviors, such as formation of multiple domains and dislocation relaxation, are observed in amorphous-phase-mediated crystallization. Theoretical calculations confirm that surface interactions can induce amorphous precipitation of metal precursors, which is analogous to the surface-induced amorphous-to-crystalline transformation occurring in biomineralization. Our results imply that an unexplored nonclassical growth mechanism is important for the formation of nanocrystals.