Direct Nanosecond Multiframe Imaging of Irreversible Dynamics in 4D Electron Microscopy.

Irreversible ultrafast events are prevalent in nature, yet their capture in real time poses significant challenges. Traditional single-shot imaging technologies, which utilize a single optical pump and single delayed electron probe, offer high spatiotemporal resolution but fail to capture the entire dynamic evolutions. Here, we introduce a novel imaging method employing a single optical pump and delayed multiple electron probes. This approach, facilitated by an innovative deflector in ultrafast electron microscopy, enables the acquisition of nine frames per exposure, paving the way for statistical and quantitative analyses. We have developed an algorithm that corrects frame-by-frame distortions, realizing a cross-correlation enhancement of ∼26%. Achieving ∼12 nm and 20 ns resolution, our method allows for the comprehensive visualization of laser-induced behaviors in Au nanoparticles, including merging, jumping, and collision processes. Our results demonstrate the capability of this multiframe imaging technique to document irreversible processes across materials science and biology with unprecedented nanometer-nanosecond precision.

Energetically Favored 2D to 3D Transition: Why Silicene Cannot Be Grown on Ag(111).

Silicene, a two-dimensional (2D) Si monolayer with properties similar to those of graphene, has attracted considerable attention because of its compatibility with existing technology. Most growth efforts to date have focused on the Ag(111) substrate, with a 3 × 3 phase widely reported below one monolayer (ML). As the coverage increases, a √3 × âˆš3 pattern frequently emerges, which has been proposed by various experimental investigations as a Si(111)-3×3-Ag reconstructed structure. We report first-principles calculations to understand this series of observations. A major finding from our energetics studies is that Si growth on Ag(111) beyond one ML will switch to the Volmer-Weber mode, forming three-dimensional sp3 films. Combining with the condition that the 3 × 3 monolayer on Ag(111) does not have the correct buckling pattern of freestanding silicene, we conclude that silicene cannot be grown on Ag(111) and that a 2D to 3D transition is energetically favored beyond one ML.

Coffee-Ring Mediated Thinning and Thickness-Dependent Dewetting Modes in Printed Polymer Droplets Coupled with Assembly of Quantum Dots for Anti-Counterfeiting.

Molecular transport processes in printed polymer droplets hold enormous importance for understanding wetting phenomena and designing systems in applications such as encoding, electronics, photonics, and sensing. This paper studies thickness-dependent dewetting modes that are activated by thermal annealing and driven by interfacial interactions within microscopically confined polymeric features. The printing of poly(2-vinylpyridine) is performed in a regime where coffee-ring effects lead to strong thinning of the central region of the deposit. Thermal annealing leads to two different modes of dewetting that depend on the thickness of the central region. Mode I refers to the formation of randomly positioned small features surrounded by large hemispherical ones located along the periphery of the printed features and occurs when the central regions are thin. Observed at large central thicknesses, Mode II mediates significant molecular transport from edges toward the center of the printed droplet with thermal annealing and forms a hemispherical feature from the initial ring-like deposit. The selective adsorption of red, green, and blue emitting quantum dots over the poly(2-vinylpyridine) results in photoluminescent patterns. The selective assembly of photoluminescent quantum dots over patterned surfaces leads to deterministic and stochastic features beneficial to creating security labels for anti-counterfeiting applications.

Multi-Scale Superhydrophobic Surface with Excellent Stability and Solar-Thermal Performance for Highly Efficient Anti-Icing and Deicing.

Ice accretion can significantly impact the efficiency and safety of outdoor equipment. Solar-thermal superhydrophobic surface is an effective strategy for anti-icing and deicing. However, droplets easily turn to the Wenzel state during the icing and melting cycle processes, significantly increasing the adhesion and making the droplets difficult to remove from the surface. In this work, a triple-scale solar-thermal superhydrophobic surface is prepared on stainless steel 304 by etching, in situ oxidation, and spin-coating TiN nanoparticles for highly efficient deicing and anti-icing. The multi-scale structure enabled the droplets to recover the Cassie state completely after melting. The contact angle decreased from 162.5° to 136.7° during the icing process and gradually increased to 162.1° during the melting process. In addition, metal oxides and TiN nanoparticles enabled the superhydrophobic surface to exhibit a high solar absorptivity ( α ¯ solar ${{\bar{\alpha }}_{{\mathrm{solar}}}}$ = 0.925). The synergistic effect of the superhydrophobicity and the solar-thermal performance endowed the designed multi-scale surface with excellent anti-icing and deicing performance. This work contributed to the practical development of anti-icing and deicing applications based on solar-thermal superhydrophobic surfaces.

Creation of Multi-Principal Element Alloy NiCoCr Nanostructures via Nanosecond Laser-Induced Dewetting.

The multi-principal element alloy nanoparticles (MPEA NPs), a new class of nanomaterials, present a highly rewarding opportunity to explore new or vastly different functional properties than the traditional mono/bi/multimetallic nanostructures due to their unique characteristics of atomic-level homogeneous mixing of constituent elements in the nanoconfinements. Here, the successful creation of NiCoCr nanoparticles, a well-known MPEA system is reported, using ultrafast nanosecond laser-induced dewetting of alloy thin films. Nanoparticle formation occurs by spontaneously breaking the energetically unstable thin films in a melt state under laser-induced hydrodynamic instability and subsequently accumulating in a droplet shape via surface energy minimization. While NiCoCr alloy shows a stark contrast in physical properties compared to individual metallic constituents, i.e., Ni, Co, and Cr, yet the transient nature of the laser-driven process facilitates a homogeneous distribution of the constituents (Ni, Co, and Cr) in the nanoparticles. Using high-resolution chemical analysis and scanning nanodiffraction, the environmental stability and grain arrangement in the nanoparticles are further investigated. Thermal transport simulations reveal that the ultrashort (≈100 ns) melt-state lifetime of NiCoCr during the dewetting event helps retain the constituent elements in a single-phase solid solution with homogenous distribution and opens the pathway to create the unique MPEA nanoparticles with laser-induced dewetting process.

Analyte-dependent Rabi splitting in solid-state plexcitonic sensors based on plasmonic nanoislands strongly coupled to J-aggregates.

A key challenge in the field of plexcitonic quantum devices is the fabrication of solid-state, device-friendly plexcitonic nanostructures using inexpensive and scalable techniques. Lithography-free, bottom-up nanofabrication methods have remained relatively unexplored within the context of plexcitonic coupling. In this work, a plexcitonic system consisting of thermally dewetted plasmonic gold nanoislands (AuNI) coated with a thin film of J-aggregates was investigated. Control over nanoisland size and morphology allowed for a range of plasmon resonances with variable detuning from the exciton. The extinction spectra of the hybrid AuNI/J-aggregate films display clear splitting into upper and lower hybrid resonances, while the dispersion curve shows anti-crossing behavior with an estimated Rabi splitting of 180 eV at zero detuning. As a proof of concept for quantum sensing, the AuNI/J-aggregate hybrid was demonstrated to behave as a plexcitonic sensor for hydrochloric acid vapor analyte. This work highlights the possibility of using thermally dewetted nanoparticles as a platform for high-quality, tunable, cost-effective, and scalable plexcitonic nanostructures for sensing devices and beyond.

Identifying hydrophobic protein patches to inform protein interaction interfaces.

Interactions between proteins lie at the heart of numerous biological processes and are essential for the proper functioning of the cell. Although the importance of hydrophobic residues in driving protein interactions is universally accepted, a characterization of protein hydrophobicity, which informs its interactions, has remained elusive. The challenge lies in capturing the collective response of the protein hydration waters to the nanoscale chemical and topographical protein patterns, which determine protein hydrophobicity. To address this challenge, here, we employ specialized molecular simulations wherein water molecules are systematically displaced from the protein hydration shell; by identifying protein regions that relinquish their waters more readily than others, we are then able to uncover the most hydrophobic protein patches. Surprisingly, such patches contain a large fraction of polar/charged atoms and have chemical compositions that are similar to the more hydrophilic protein patches. Importantly, we also find a striking correspondence between the most hydrophobic protein patches and regions that mediate protein interactions. Our work thus establishes a computational framework for characterizing the emergent hydrophobicity of amphiphilic solutes, such as proteins, which display nanoscale heterogeneity, and for uncovering their interaction interfaces.

Reversible Surface Energy Storage in Molecular-Scale Porous Materials.

Forcible wetting of hydrophobic pores represents a viable method for energy storage in the form of interfacial energy. The energy used to fill the pores can be recovered as pressure-volume work upon decompression. For efficient recovery, the expulsion pressure should not be significantly lower than the pressure required for infiltration. Hysteresis of the wetting/drying cycle associated with the kinetic barrier to liquid expulsion results in energy dissipation and reduced storage efficiency. In the present work, we use open ensemble (Grand Canonical) Monte Carlo simulations to study the improvement of energy recovery with decreasing diameters of planar pores. Near-complete reversibility is achieved at pore widths barely accommodating a monolayer of the liquid, thus minimizing the area of the liquid/gas interface during the cavitation process. At the same time, these conditions lead to a steep increase in the infiltration pressure required to overcome steric wall/water repulsion in a tight confinement and a considerable reduction in the translational entropy of confined molecules. In principle, similar effects can be expected when increasing the size of the liquid particles without altering the absorbent porosity. While the latter approach is easier to follow in laboratory work, we discuss the advantages of reducing the pore diameter, which reduces the cycling hysteresis while simultaneously improving the stored-energy density in the material.

Molecular Dynamics Simulations of High-Performance, Dissipationless Desalination across Self-Assembled Amyloid Beta Nanotubes.

Climate change is causing droughts and water shortages. Membrane desalination is one of the most widely employed conventional methods of creating a source of clean water, but is a very energy-intensive process. Membrane separation requires high salt selectivity across nano-channels, yet traditional techniques remain inefficient in this regard. Herein, a bioinspired, chemically robust, amyloid-fibril-based nanotube is designed, exhibiting water permeability and salt rejection properties capable of providing highly efficient desalination. Molecular dynamics simulations show that nano-dewetting facilitates the unidirectional motion of water molecules on the surface of amyloid beta (Aß) sheets owing to the ratchet structure of the underlying potential surface and the broken detailed balance. The water inside the self-assembled Aß nanotube (ABNT) overflows, while the passage of salts can be blocked using amphiphilic peptides. The designed nanofilter ABNT shows 100% desalination efficiency with perfect NaCl rejection. The production of ≈2.5 tons of pure water per day without any energy input, which corresponds to a water flux up to 200 times higher than those of existing commercial methods, is assessed by this simulation method. These results provide a detailed fundamental understanding of potential high-performance nanotechnologies for water treatment.

Spontaneous Dewetting of Au-Thin Layers on Oxide- and Fluorine-Terminated Single Crystalline Anatase and Efficient Use in Photocatalytic H2 Production.

In the present work, the spontaneous dewetting of thin Au layers on single crystalline anatase nanosheets into narrow-disperse Au nanoparticles is investigated. Patterns of the Au particles can be formed on the main facets of anatase that provide a high co-catalytic activity for photocatalytic generation of H2 . Dewetting is distinctly influenced by the respective facets (001) and (101), the deposit thickness, and secondary thermal dewetting, but most strongly by the surface termination of the nanosheets. Fluoride termination not only leads to an enhanced Au-phobic behavior but strongly affects the co-catalytic activity for photocatalytic generation of H2 . While fluoride termination with or without Au decoration is detrimental for hole transfer, the interplay of the Au co-catalyst and surface fluoride yields highly beneficial effect for electron transfer. This results in a three-times higher photocatalytic H2 production for the F-terminated surface. The findings suggest that dewetting of Au on surface fluorinated TiO2 is an effective way to modulate surface dewetting and achieve a strongly enhanced photocatalytic activity.

Dewetting Behavior of Random Copolymer Films Induced by Solvent Vapor Annealing.

In recent years, the dewetting behavior of block copolymer films has been studied a lot, but that of random copolymer films was rarely studied. In this study, effects of film thickness and solvent vapor annealing duration (0 s-24 h) on the dewetting behavior of the spin-coated poly(styrene-co-acrylonitrile) (SAN) random copolymer films were mainly investigated by atomic force microscopy and contact angle method for the first time. The film thicknesses of the SAN films prepared at different concentrations were characterized by X-ray reflectometry to be 6-34 nm. With the annealing of acetone vapor, the SAN films first appear holes and then rupture into droplets which fuse and break periodically. The periodic evolutions of the droplets are due to the preferred affinity of acetone molecules with the AN segments and the change of surface energy. This phenomenon is different from the single evolutions in the spin-coated polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) block copolymer films. This illustrates the interactions between AN segments and the substrate are stronger than those between PMMA segments and the substrate in the spin-coated films.

Dynamical control by water at a molecular level in protein dimer association and dissociation.

Water, often termed as the "lubricant of life," is expected to play an active role in navigating protein dissociation-association reactions. In order to unearth the molecular details, we first compute the free-energy surface (FES) of insulin dimer dissociation employing metadynamics simulation, and then carry out analyses of insulin dimerization and dissociation using atomistic molecular-dynamics simulation in explicit water. We select two sets of initial configurations from 1) the dissociated state and 2) the transition state, and follow time evolution using several long trajectories (∼1-2 µs). During the process we not only monitor configuration of protein monomers, but also the properties of water. Although the equilibrium structural properties of water between the two monomers approach bulklike characteristics at a separation distance of ∼5 nm, the dynamics differ considerably. The complex association process is observed to be accompanied by several structural and dynamical changes of the system, such as large-scale correlated water density fluctuations, coupled conformational fluctuation of protein monomers, a dewettinglike transition with the change of intermonomeric distance RMM from ∼4 to ∼2 nm, orientation of monomers and hydrophobic hydration in the monomers. A quasistable, solvent-shared, protein monomer pair (SSPMP) forms at around 2 nm during association process which is a local free-energy minimum having ∼50-60% of native contacts. Simulations starting with arrangements sampled from the transition state (TS) of the dimer dissociation reveal that the final outcome depends on relative orientation of the backbone in the "hotspot" region.

Experimental and Computational Study of the Orientation Dependence of Single-Crystal Ruthenium Nanowire Stability.

Single-crystal nanowires are of broad interest for applications in nanotechnology. However, such wires are subject to both the Rayleigh-Plateau instability and an ovulation process that are expected to lead to their break up into particle arrays. Single crystal Ru nanowires were fabricated with axes lying along different crystallographic orientations. Wires bound by equilibrium facets along their length did not break up through either a Rayleigh-Plateau or ovulation process, while wires with other orientations broke up through a combination of both. Mechanistic insight is provided using a level-set simulation that accounts for strongly anisotropic surface energies, providing a framework for design of morphologically stable nanostructures.

Dual-Dewetting Process for Self-Assembled Nanoparticle Clusters in Wafer Scale.

Plasmonic molecules, which are geometrically well-defined plasmonic metal nanoparticle clusters, have attracted significant attention due to their enhancement of light-matter interactions owing to a stronger electric field enhancement than that by single particles. High-resolution lithography techniques provide precise positioning of plasmonic nanoparticles, but their fabrication costs are excessively high. In this study, we propose a lithography-free, self-assembly fabrication method, termed the dual-dewetting process, which allows the control of the size and density of gold nanoparticles. This process involves depositing a gold thin film on a substrate and inducing dewetting through thermal annealing, followed by a second deposition and annealing. The method achieves a uniform distribution of particle size and density, along with increased particle density, across a 6-inch wafer. The superiority of the method is confirmed by a 30-fold increase in the signal intensity of surface-enhanced Raman scattering following the additional dewetting with an 8 nm film, compared to single dewetting alone. Our findings indicate that the dual-dewetting method provides a simple and efficient approach to enable a variety of plasmonic applications through efficient plasmonic molecule large-area fabrication.

Formation of Au, Pt, and bimetallic Au-Pt nanostructures from thermal dewetting of single-layer or bilayer thin films.

Formation of Au, Pt, and bimetallic Au-Pt nanostructures by thermal dewetting of single-layer Au, Pt and bilayer Au-Pt thin films on Si substrates was systematically studied. The solid-state dewetting of both single-layer and bilayer metallic films was shown to go through heterogeneous void initiation followed by void growth via capillary agglomeration. For the single-layer of Au and Pt films, the void growth started at a temperature right above the Hüttig temperature, at which the atoms at the surface or at defects become mobile. Uniformly distributed Au (7 ± 1 nm to 33 ± 8 nm) and Pt (7 ± 1 nm) NPs with monodispersed size distributions were produced from complete dewetting achieved for thinner 1.7-5.5 nm thick Au and 1.4 nm thick Pt films, respectively. The NP size is strongly dependent on the initial thin film thickness, but less so on temperature and time. Thermal dewetting of Au-Pt bilayer films resulted in partial dewetting only, forming isolated nano-islands or large particles, regardless of sputtering order and total thin film thickness. The increased resistance to thermal dewetting shown in the Au-Pt bilayer films as compared to the individual Au or Pt layer is a reflection of the stabilizing effect that occurs upon adding Pt to Au in the bimetallic system. Energy dispersive x-ray spectroscopic analysis showed that the two metals in the bilayer films broke up together instead of dewetting individually. According to the x-ray diffraction analysis, the produced Au-Pt nanostructures are phase-segregated, consisting of an Au-rich phase and a Pt-rich phase.

A low-cost self-dispersing method of droplet array generation enabled by a simple reusable mask for bioanalysis and bioassays.

Discontinuous dewetting is an attractive technique that can produce droplet array of specific volume, geometry and at predefined location on a substrate. Droplet array has great potential in bioanalysis such as high-throughput live cell screening, digital PCR, and drug candidates. Here, we propose a self-dispersing droplet array generation method, which has advantages of low cost, simple operation, and easy large-area production ability. Droplet array of specific volumes was generated on a polymethyl methacrylate (PMMA) substrate using a simple reusable polyimide (PI) adhesive mask. Experiment shows that the generated droplet array can be used to successfully capture single particles which obeys Poisson distribution in a high-throughput manner. Furthermore, a droplet-array sandwiching chip was created based on the self-dispersion method for rapid detection of human serum albumin (HSA) at wide range of 183-11,712 µg/mL with low reagent consumption of 2.2 µL, demonstrating its potential applications in convenient high-throughput bioanalysis and bioassays.

Signatures of slip in dewetting polymer films.

Thin polymer films on hydrophobic substrates are susceptible to rupture and hole formation. This, in turn, initiates a complex dewetting process, which ultimately leads to characteristic droplet patterns. Experimental and theoretical studies suggest that the type of droplet pattern depends on the specific interfacial condition between the polymer and the substrate. Predicting the morphological evolution over long timescales and on the different length scales involved is a major computational challenge. In this study, a highly adaptive numerical scheme is presented, which allows for following the dewetting process deep into the nonlinear regime of the model equations and captures the complex dynamics, including the shedding of droplets. In addition, our numerical results predict the previously unknown shedding of satellite droplets during the destabilization of liquid ridges that form during the late stages of the dewetting process. While the formation of satellite droplets is well known in the context of elongating fluid filaments and jets, we show here that, for dewetting liquid ridges, this property can be dramatically altered by the interfacial condition between polymer and substrate, namely slip. This work shows how dissipative processes can be used to systematically tune the formation of patterns.

Plasmonic and Conductive Structures of TCO Films with Embedded Cu Nanoparticles.

Cu nanoparticles were produced by using solid-state dewetting (dry) of a 1.3 nm Cu layer or laser ablation of a Cu solid target (wet) in acetone and methanol. The morphology and chemical composition of the nanoparticles were investigated as a function of the synthesis methods and their key parameters of the annealing temperature (200-500 °C) and the liquid environment during the ablation. Cu nanoparticles were then embedded in transparent conductive oxide (TCO) films as aluminum-doped zinc oxide (AZO) or zirconium-doped indium oxide (IZrO); the TCObott/Cu nanoparticle/TCOtop structures were synthesized with all combinations of AZO and IZrO as the top and bottom layers. The goal was to achieve a plasmonic and conductive structure for photovoltaic applications via a comparison of the involved methods and all fabricated structures. In particular, solid-state dewetting produced faceted or spherical (depending on the annealing temperature) nanoparticles with an average size below 150 nm while laser ablation produced spherical nanoparticles below 250 nm. Dry and wet plasmonic conductive structures as a function of the TCOs employed and the temperature of annealing could reach a sheet resistance of 86 Ω/sq. The energy band-gap Egap, absorbance, transmittance, and reflectance of the plasmonic conductive structures were investigated in the UV-vis-NIR range. They showed a dependence on the sequence of the top and bottom TCO, with best transmittances of 89.4% for the dry plasmonic conductive structure and 84.7% for the wet plasmonic conductive structure. The latter showed a higher diffused transmittance of between 10-20% in the visible range.

Pulsed laser-induced dewetting and thermal dewetting of Ag thin films for the fabrication of Ag nanoparticles.

Two different dewetting methods, namely pulsed laser-induced dewetting (PLiD)-a liquid-state dewetting process and thermal dewetting (TD)-a solid-state dewetting process, have been systematically explored for Ag thin films (1.9-19.8 nm) on Si substrates for the fabrication of Ag nanoparticles (NPs) and the understanding of dewetting mechanisms. The effect of laser fluence and irradiation time in PLiD and temperature and duration in TD were investigated. A comparison of the produced Ag NP size distributions using the two methods of PLiD and TD has shown that both produce Ag NPs of similar size with better size uniformity for thinner films (<6 nm), whereas TD produced bigger Ag NPs for thicker films (≥8-10 nm) as compared to PLiD. As the film thickness increases, the Ag NP size distributions from both PLiD and TD show a deviation from the unimodal distributions, leading to a bimodal distribution. The PLiD process is governed by the mechanism of nucleation and growth of holes due to the formation of many nano-islands from the Volmer-Weber growth of thin films during the sputtering process. The investigation of thickness-dependent NP size in TD leads to the understanding of void initiation due to pore nucleation at the film-substrate interface. Furthermore, the linear dependence of NP size on thickness in TD provides direct evidence of fingering instability, which leads to the branched growth of voids.

Self-organization of random copolymers to nanopatterns by localized e-beam dosing.

Strategic electron beam (e-beam) irradiation on the surface of an ultrathin (<100 nm) film of polystyrene-poly(methyl methacrylate) (PS-PMMA) random copolymer followed by solvent annealing stimulates a special variety of dewetting, leading to large-area hierarchical nanoscale patterns. For this purpose, initially, a negative (positive) tone of resist PS (PMMA) under weak e-beam exposure is exploited to produce an array of sites composed of cross-linked PS (chain-scissioned PMMA). Subsequently, annealing with the help of a developer solvent engenders dewetted patterns in the exposed zones where PMMA blocks are confined by the blocks of cross-linked PS. The e-beam dosage was systematically varied from 180µC cm-2to 10 000µC cm-2to explore the tone reversal behavior of PMMA on the dewetted patterns. Remarkably, at relatively higher e-beam dosing, both PMMA and PS blocks act as negative tones in the exposed zone. In contrast, the chain scission of PMMA in the periphery of the exposed regions due to scattered secondary electrons caused confined dewetting upon solvent annealing. Such occurrences eventually lead to pattern miniaturization an order of magnitude greater than with conventional thermal or solvent vapor annealed dewetting. Selective removal of PMMA blocks of RCP using a suitable solvent provided an additional 50% reduction in the size of the dewetted features.