Dynamics of thin precursor film in wetting of nanopatterned surfaces.

The spreading of a liquid droplet on flat surfaces is a well-understood phenomenon, but little is known about how liquids spread on a rough surface. When the surface roughness is of the nanoscopic length scale, the capillary forces dominate and the liquid droplet spreads by wetting the nanoscale textures that act as capillaries. Here, using a combination of advanced nanofabrication and liquid-phase transmission electron microscopy, we image the wetting of a surface patterned with a dense array of nanopillars of varying heights. Our real-time, high-speed observations reveal that water wets the surface in two stages: 1) an ultrathin precursor water film forms on the surface, and then 2) the capillary action by nanopillars pulls the water, increasing the overall thickness of water film. These direct nanoscale observations capture the previously elusive precursor film, which is a critical intermediate step in wetting of rough surfaces.

Visualizing the Conversion of Metal-Organic Framework Nanoparticles into Hollow Layered Double Hydroxide Nanocages.

Hollow layered double hydroxide (LDH) nanostructures derived from metal-organic framework (MOF) nanoparticles (NPs) are candidate materials for applications in catalysis and energy storage. MOF NPs serve as a sacrificial template and are converted into LDH nanomaterials through two simultaneous processes: etching of the NPs and growth of LDHs on the NP surfaces. However, for these conversion processes, early reaction stages, intermediate products, and details of their reaction kinetics are still unknown. Using liquid-phase transmission electron microscopy (TEM), we show that cubic and rhombic dodecahedron (RD) ZIF-8 NPs convert into hollow LDH nanocages via the nucleation and growth of LDH nanosheets on their surface as the MOF NPs gradually etch. These direct in situ observations reveal that, in these reactions, maintaining comparable etching and growth rates is key to forming well-defined hollow nanostructures that retain the shape of the underlying MOF NP template. Our study provides a critical insight pivotal to the design and synthesis of complex MOF-derived hollow nanomaterials.

Direct Observations of the Rotation and Translation of Anisotropic Nanoparticles Adsorbed at a Liquid-Solid Interface.

We can learn about the interactions between nanoparticles (NPs) in solution and solid surfaces by tracking how they move. Here, we use liquid cell transmission electron microscopy (TEM) to follow directly the translation and rotation of Au nanobipyramids (NBPs) and nanorods (NRs) adsorbed onto a SiN x surface at a rate of 300 frames per second. This study is motivated by the enduring need for a detailed description of NP motion on this common surface in liquid cell TEM. We will show that NPs move intermittently on the time scales of milliseconds. First, they rotate in two ways: (1) rotation around the center of mass and (2) pivoted rotation at the tips. These rotations also lead to different modes of translation. A NP can move through small displacements in the direction roughly parallel to its body axis (shuffling) or with larger steps via multiple tip-pivoted rotations. Analysis of the trajectories indicates that both displacements and rotation angles follow heavy-tailed power law distributions, implying anomalous diffusion. The spatial and temporal resolution afforded by our approach also revealed differences between the different NPs. The 50 nm NRs and 100 nm NBPs moved with a combination of shuffles and rotation-mediated displacements after illumination by the electron beam. With increasing electron fluence, 50 nm NRs also started to move via desorption-mediated jumps. The 70 nm NRs did not exhibit translational motion and only made small rotations. These results describe how NP dynamics evolve under the electron beam and how intermittent pinning and release at specific adsorption sites on the solid surface control NP motion at the liquid-solid interface. We also discuss the effect of SiN x surface treatment on NP motion, demonstrating how our approach can provide broader insights into interfacial transport.

In Situ Kinetic and Thermodynamic Growth Control of Au-Pd Core-Shell Nanoparticles.

One-pot wet-chemical synthesis is a simple way to obtain nanoparticles (NPs) with a well-defined shape and composition. However, achieving good control over NP synthesis would require a comprehensive understanding of the mechanisms of NP formation, something that is challenging to obtain experimentally. Here, we study the formation of gold (Au) core-palladium (Pd) shell NPs under kinetically and thermodynamically controlled reaction conditions using in situ liquid cell transmission electron microscopy (TEM). By controlling the reaction temperature, we demonstrate that it is possible to tune the shape of Au nanorods to Au-Pd arrow-headed structures or to cuboidal core-shell NPs. Our in situ studies show that the reaction temperature can switch the Pd shell growth between the kinetically and thermodynamically dominant regimes. The mechanistic insights reported here reveal how the reaction temperature affects the packing of the capping agents and how the facet selection of depositing shell atoms drives the shell formation under different kinetic conditions, which is useful for synthesizing NPs with greater design flexibility in shape and elemental composition for various technological applications.

Spontaneous Reshaping and Splitting of AgCl Nanocrystals under Electron Beam Illumination.

AgCl is photosensitive and thus often used as micromotors. However, the dynamics of individual AgCl nanoparticle motion in liquids upon illumination remains elusive. Here, using liquid cell transmission electron microscope (TEM), AgCl nanocrystals reshaping and splitting spontaneously in an aqueous solution under electron beam illumination are observed. It is found that the AgCl nanocrystals are negatively charged in the liquid environment, where the charge induces a repulsive Coulomb force that reshapes and stretches those nanocrystals. Upon extensive stretching, the AgCl nanocrystal splits into small nanocrystals and each nanocrystal retracts back into cuboid shapes due to the cohesive surface. This analysis shows that each nanocrystal maintains a single crystal rocksalt structure during splitting. The splitting of AgCl nanocrystals is analogous to the electrified liquid droplets or other reported the Coulomb fission phenomenon, but with distinctive structural properties. Revealing of the dynamic behavior of AgCl nanocrystals opens the opportunity to explore their potential applications as actuators for nanodevices.

Transient Clustering of Reaction Intermediates during Wet Etching of Silicon Nanostructures.

Wet chemical etching is a key process in fabricating silicon (Si) nanostructures. Currently, wet etching of Si is proposed to occur through the reaction of surface Si atoms with etchant molecules, forming etch intermediates that dissolve directly into the bulk etchant solution. Here, using in situ transmission electron microscopy (TEM), we follow the nanoscale wet etch dynamics of amorphous Si (a-Si) nanopillars in real-time and show that intermediates generated during alkaline wet etching first aggregate as nanoclusters on the Si surface and then detach from the surface before dissolving in the etchant solution. Molecular dynamics simulations reveal that the molecules of etch intermediates remain weakly bound to the hydroxylated Si surface during the etching and aggregate into nanoclusters via surface diffusion instead of directly diffusing into the etchant solution. We confirmed this model experimentally by suppressing the formation of nanoclusters of etch intermediates on the Si surfaces by shielding the hydroxylated Si sites with large ions. These results suggest that the interaction of etch intermediates with etching surfaces controls the solubility of reaction intermediates and is an important parameter in fabricating densely packed clean 3D nanostructures for future generation microelectronics.

Hydration Layer-Mediated Pairwise Interaction of Nanoparticles.

When any two surfaces in a solution come within a distance the size of a few solvent molecules, they experience a solvation force or a hydration force when the solvent is water. Although the range and magnitude of hydration forces are easy to characterize, the effects of these forces on the transient steps of interaction dynamics between nanoscale bodies in solution are poorly understood. Here, using in situ transmission electron microscopy, we show that when two gold nanoparticles in water approach each other at a distance within two water molecules (∼5 Å), which is the combined thickness of the hydration shell of each nanoparticle, they form a sterically stabilized transient nanoparticle dimer. The interacting surfaces of the nanoparticles come in contact and undergo coalescence only after these surfaces are fully dehydrated. Our observations of transient steps in nanoparticle interactions, which reveal the formation of hydration layer mediated metastable nanoparticle pairs in solution, have significant implications for many natural and industrial processes.

Nanodroplet-Mediated Assembly of Platinum Nanoparticle Rings in Solution.

Soft fluidlike nanoscale objects can drive nanoparticle assembly by serving as a scaffold for nanoparticle organization. The intermediate steps in these template-directed nanoscale assemblies are important but remain unresolved. We used real-time in situ transmission electron microscopy to follow the assembly dynamics of platinum nanoparticles into flexible ringlike chains around ethylenediaminetetraacetic acid nanodroplets dispersed in solution. In solution, these nanoring assemblies form via sequential attachment of the nanoparticles to binding sites located along the circumference of the nanodroplets, followed by the rearrangement and reorientation of the attached nanoparticles. Additionally, larger nanoparticle ring assemblies form via the coalescence of smaller ring assemblies. The intermediate steps of assembly reported here reveal how fluidlike nanotemplates drive nanoparticle organization, which can aid the future design of new nanomaterials.

CTAB-Influenced Electrochemical Dissolution of Silver Dendrites.

Dendrite formation on the electrodes of a rechargeable battery during the charge-discharge cycle limits its capacity and application due to short-circuits and potential ignition. However, understanding of the underlying dendrite growth and dissolution mechanisms is limited. Here, the electrochemical growth and dissolution of silver dendrites on platinum electrodes immersed in an aqueous silver nitrate (AgNO3) electrolyte solution was investigated using in situ liquid-cell transmission electron microscopy (TEM). The dissolution of Ag dendrites in an AgNO3 solution with added cetyltrimethylammonium bromide (CTAB) surfactant was compared to the dissolution of Ag dendrites in a pure aqueous AgNO3 solution. Significantly, when CTAB was added, dendrite dissolution proceeded in a step-by-step manner, resulting in nanoparticle formation and transient microgrowth stages due to Ostwald ripening. This resulted in complete dissolution of dendrites and "cleaning" of the cell of any silver metal. This is critical for practical battery applications because "dead" lithium is known to cause short circuits and high-discharge rates. In contrast to this, in a pure aqueous AgNO3 solution, without surfactant, dendrites dissolved incompletely back into solution, leaving behind minute traces of disconnected silver particles. Finally, a mechanism for the CTAB-influenced dissolution of silver dendrites was proposed based on electrical field dependent binding energy of CTA(+) to silver.

Bonding pathways of gold nanocrystals in solution.

Nanocrystal bonding is an important phenomenon in crystal growth and nanoscale welding. Here, we show that for gold nanocrystals bonding in solution can follow two distinct pathways: (1) coherent, defect-free bonding occurs when two nanocrystals attach with their lattices aligned to within a critical angle; and (2) beyond this critical angle, defects form at the interfaces where the nanocrystals merge. The critical misalignment angle for ∼10 nm crystals is ∼15° in both in situ experiments and full-atom molecular dynamics simulations. Understanding the origin of this critical angle during bonding may help us predict and manage strain profiles in nanoscale assemblies and inspire techniques toward reproducible and extensible architectures using only basic crystalline blocks.

Trends in the prevalence and social determinants of stunting in India, 2005-2021: findings from three rounds of the National Family Health Survey.

Objectives: To assess social determinants of stunting and the shifts in contributions of socio-demographic factors to national prevalence trends in India between 2005 and 2021. Methods: We leveraged data from three rounds of the National Family Health Survey (NFHS-3: 2005-2006, NFHS-4: 2015-2016, NFHS-5: 2019-2021) for 443 038 children under 5 years. Adjusted logistic regression models and a Kitigawa-Oaxaca-Blinder decomposition were deployed to examine how wealth, residence, belonging to a marginalised social group, maternal education and child sex contributed to changes in stunting prevalence. Results: The decrease in stunting prevalence was notably slower between NFHS-4 and NFHS-5 (annual average rate of reduction (AARR): 1.33%) than between NFHS-3 and NFHS-4 (AARR: 2.20%). The protective effect of high wealth diminished from 2015 onwards but persisted for high maternal education. However, an intersection of higher household wealth and maternal education mitigated stunting to a greater extent than either factor in isolation. Residence only predicted stunting in 2005-2006 with an urban disadvantage (adjusted OR: 1.18; 95% CI: 1.07 to 1.29). Children from marginalised social groups displayed increased likelihoods of stunting, from 6-16% in 2005-2006 to 11-21% in 2015-2016 and 2020-2021. Being male was associated with 6% and 7% increased odds of stunting in 2015-2016 and 2019-2021, respectively. Increased household wealth (45%) and maternal education (14%) contributed to decreased stunting prevalence between 2005 and 2021. Conclusions: Stunting prevalence in India has decreased across social groups. However, social disparities in stunting persist and are exacerbated by intersections of low household wealth, maternal education and being from a marginalised social group. Increased survival must be accompanied by needs-based interventions to support children and mitigate mutually reinforcing sources of inequality.

Preventing the Capillary-Induced Collapse of Vertical Nanostructures.

Robust processes to fabricate densely packed high-aspect-ratio (HAR) vertical semiconductor nanostructures are important for applications in microelectronics, energy storage and conversion. One of the main challenges in manufacturing these nanostructures is pattern collapse, which is the damage induced by capillary forces from numerous solution-based processes used during their fabrication. Here, using an array of vertical silicon (Si) nanopillars as test structures, we demonstrate that pattern collapse can be greatly reduced by a solution-phase deposition method to coat the nanopillars with self-assembled monolayers (SAMs). As the main cause for pattern collapse is strong adhesion between the nanopillars, we systematically evaluated SAMs with different surface energy components and identified H-bonding between the surfaces to have the largest contribution to the adhesion. The advantage of the solution-phase deposition method is that it can be implemented before any drying step, which causes patterns to collapse. Moreover, after drying, these SAMs can be easily removed using a gentle air-plasma treatment right before the next fabrication step, leaving a clean nanopillar surface behind. Therefore, our approach provides a facile and effective method to prevent the drying-induced pattern collapse in micro- and nanofabrication processes.

Nanoscale Elastocapillary Effect Induced by Thin-Liquid-Film Instability.

Dense arrays of high-aspect-ratio (HAR) vertical nanostructures are essential elements of microelectronic components, photovoltaics, nanoelectromechanical, and energy storage devices. One of the critical challenges in manufacturing the HAR nanostructures is to prevent their capillary-induced aggregation during solution-based nanofabrication processes. Despite the importance of controlling capillary effects, the detailed mechanisms of how a solution interacts with nanostructures are not well understood. Using in situ liquid cell transmission electron microscopy (TEM), we track the dynamics of nanoscale drying process of HAR silicon (Si) nanopillars in real-time and identify a new mechanism responsible for pattern collapse and nanostructure aggregation. During drying, deflection and aggregation of nanopillars are driven by thin-liquid-film instability, which results in much stronger capillary interactions between the nanopillars than the commonly proposed lateral meniscus interaction forces. The importance of thin-film instability in dewetting has been overlooked in prevalent theories on elastocapillary aggregation. The new dynamic mechanism revealed by in situ visualization is essential for the development of robust nanofabrication processes.

Interactions and Attachment Pathways between Functionalized Gold Nanorods.

Nanoparticle (NP) self-assembly has been recognized as an important technological process for forming ordered nanostructures. However, the detailed dynamics of the assembly processes remain poorly understood. Using in situ liquid cell transmission electron microscopy, we describe the assembly modes of gold (Au) nanorods (NRs) in solution mediated by hydrogen bonding between NR-bound cysteamine linker molecules. Our observations reveal that by tuning the linker concentration, two different NR assembly modes can be achieved. These assembly modes proceed via the (1) end-to-end and (2) side-to-side attachment of NRs at low and high linker concentrations in solution, respectively. In addition, our time-resolved observations reveal that the side-to-side NR assemblies can occur through two different pathways: (i) prealigned attachment, where two Au NRs prealign to be parallel prior to assembly, and (ii) postattachment alignment, where two Au NRs first undergo end-to-end attachment and pivot around the attachment point to form the side-to-side assembly. We attributed the observed assembly modes to the distribution of linkers on the NR surfaces and the electrostatic interactions between the NRs. The intermediate steps in the assembly reported here reveal how the shape and surface functionalities of NPs drive their self-assembly, which is important for the rational design of hierarchical nanostructures.

Nanodroplet Depinning from Nanoparticles.

Nanoscale defects on a substrate affect the sliding motion of water droplets. Using in situ transmission electron microscopy imaging, we visualized the depinning dynamics of water nanodroplets from gold nanoparticles on a flat SiNx surface. Our observations showed that nanoscale pinning effects of the gold nanoparticle oppose the lateral forces, resulting in stretching, even breakup, of the water nanodroplet. Using continuum long wave theory, we modeled the dynamics of a nanodroplet depinning from a nanoparticle of comparable length scales, and the model results are consistent with experimental findings and show formation of a capillary bridge prior to nanodroplet depinning. Our findings have important implications on surface cleaning at the nanoscale.