Surface Energy Minimization Research Articles

Oriented Epitaxial Growth of Mixed-Dimensional van der Waals Heterostructures with One-Dimensional (1D) Bi2S3 Nanowires and Two-Dimensional (2D) WS2 Monolayers for Performance-Enhanced Photodetectors.

The synthesis of mixed-dimensional van der Waals heterostructures with controlled alignment by chemical vapor deposition (CVD) technique remains a big challenge due to the complex epitaxial growth mechanism. Herein, we report the epitaxial growth of mixed-dimensional Bi2S3/WS2 heterostructures by a two-step CVD method. Bi2S3 crystals grown on 2D WS2 monolayers exhibit 1D feature with the preferred orientation, indicating a strong epitaxial growth behavior at the 1D/2D interface. Furthermore, the heterostructure was carefully characterized by transmission electron microscopy, which reveals the preferential growth of Bi2S3 nanowires along the zigzag edge of WS2 monolayers. The experimental results are also consistent with the theoretical calculations by DFT, where the preferred orientation possesses minimal surface energy. The strong interaction between Bi2S3 and WS2 enables efficient charge transfer of photogenerated carriers at the heterointerface, which leads to a largely improved light harvesting capability with the highest responsivity of ∼48.1 AW-1 and detectivity of ∼5.9 × 1012 Jones.

Wetting phenomena of droplets and gas bubbles: Contact angle hysteresis based on varying liquid-solid and solid-gas interfacial tensions.

Wetting phenomena have been widely observed in our daily lives, such as dew on lotus leaf, and applied in technical applications, e.g., ink-jet printing. In contrast to constant liquid-solid and solid-gas interfacial tensions in Young's law, we here focus on the wetting phenomena by considering varying fluid-solid interfacial tensions. We analyze the energy landscape, the map of Young's contact angle, the number and corresponding contact angle of local energy minima, and the contact angle hysteresis for a liquid droplet on a solid substrate in a gas phase. In addition, a gas bubble on a solid substrate in a liquid phase has been scrutinized from the aspect of surface energy minimization. The wetting effect has been regarded, where the liquid and gas species penetrate into the solid phase on the microscopic scale [F. Wang and B. Nestler, Phys. Rev. Lett. 132, 126202 (2024)]. We assume the liquid-solid and the solid-gas interfacial tensions to be a function dependent on the volume fraction of the liquid and the gas species and investigate the impact of the size ratio of the droplet to the solid surface that is overlooked in existing theories on the wetting phenomena. Our finding sheds light on the microscopic origin of the contact angle hysteresis and the droplet size effect on the wetting phenomena.

Self-folding of two-dimensional thin templates into pyramidal microstructures by a liquid drop: a numerical model

We present a numerical framework bringing together a structural and a surface-energy minimization model to compute nano- and microorigami self-folding processes, that are three-dimensional in nature. A liquid drop, initially at rest on the template, triggers the spontaneous folding and deforms dynamically with the template. As application, the self-folding of thin two-dimensional templates into pyramidal microstructures is simulated. Each template is composed of a fixed regular base connected to rigid triangular side panels by two elastic hinges. We presently determine the condition, at which the transition from partial to full drop encapsulation occurs. The present model makes use of phase fields to numerically represent the drop and the template. This allows to: (i) develop an efficient computational method, which incorporates time-derivative terms and (ii) study three-dimensional complex self-folding processes.

Zinc blende ZnS (001) surface structure investigated by XPS, LEED, and DFT

The formation and stability of the zinc blende ZnS (001) single crystal surface have been examined by x-ray photoemission spectroscopy (XPS), low-energy electron diffraction (LEED), and density-functional theory (DFT) calculations. LEED patterns obtained from the ZnS (001) surface prepared in ultrahigh vacuum conditions at 1420 K reveal the formation of a (1 × 2) reconstructed structure. Surface chemical characterization performed by XPS indicates that the surface region consists of a Zn-deficient (sulfur-rich) phase. Our DFT theoretical calculations confirm that the ZnS (001) (1x2) surface structure is energetically favorable and consists of a Zn-terminated topmost surface layer stabilized by Zn-vacancies. The calculations also suggest that the remaining Zn-cations on the surface are displaced inward, driven by surface energy minimization related to zinc-blend ZnS (001) polar nature. Notably, the observed surface structural modifications have potential implications for the ZnS physical and chemical properties.

Pinning Forces on the Omniphobic Dry, Liquid-Infused, and Liquid-Attached Surfaces.

Omniphobic coatings effectively repelling water, oils, and other liquids are of great interest and have a broad number of applications including self-cleaning, anti-icing surfaces, biofouling protection, selective filtration, etc. To create such coatings, one should minimize the pinning force that resists droplet motion and causes contact angle hysteresis. The minimization of the free surface energy by means of the chemical modification of the solid surface is not enough to obtain a nonsticky slippery omniphobic surface. One should minimize the contact between the solid and the droplet. Besides coating the surface with flat polymer films, among the major approaches to create omniphobic coatings, one can reveal "lotus effect" textured coatings, slippery liquid-infused porous surfaces (SLIPS), and slippery omniphobic covalently attached liquid (SOCAL) coatings. It is possible to turn one surface type into other by texturizing, impregnating with liquids, or grafting flexible liquid-like polymer chains. There are a number of models describing the pinning force on surfaces, but the transitions between states with different wetting regimes remain poorly understood. At the same time, such studies can significantly broaden existing ideas about the physics of wetting, help to design coatings, and also contribute to the development of generalized models of the pinning force. Here we review the existing pinning force (contact angle hysteresis) models on various omniphobic substrates. Also, we discuss the current studies of the pinning force in the transitions between different wetting regimes.

Synthesis and properties of silicone-modified polyurethane acrylate for magnetically driven blue light photocurable superhydrophobic coatings

A low surface energy silicone-modified polyurethane acrylate (Si-PUA) has been synthesized and employed as the primary constituent for the magnetically driven photocurable coatings. By integrating magnetically driven assembly technology with blue light photocuring technology, a superhydrophobic coating featuring low surface energy and micro/nano rough structures was successfully fabricated. The influences of hydroxy-terminated polydimethylsiloxane (PDMS) content and the R-value (-NCO/-OH) on the performance of PUA and coating systems were investigated using Photo-DSC, TGA, rheology, tensile testing machine, and SEM-EDS. The molecular structure of Si-PUA was characterized using FT-IR and 1HNMR. The result revealed that the composite coating exhibited a minimum surface energy when the PDMS content was 5 wt% and the R-value was 1.6, resulting in a surface free energy of 24 mJ/m2. When the coating formulation consists of a Si-PUA:HEA ratio of 7:3, an initiator dosage of 2% (with CQ/EDB at a 1:1 ratio), and a carbonyl iron powder (CIP) content of 100 wt%, the resulting photocured film exhibits a surface contact angle of 157.6° and a rolling angle of 5°, thereby satisfying the superhydrophobicity standard.

Diameter-dependent phase selectivity in 1D-confined tungsten phosphides

Topological materials confined in 1D can transform computing technologies, such as 1D topological semimetals for nanoscale interconnects and 1D topological superconductors for fault-tolerant quantum computing. As such, understanding crystallization of 1D-confined topological materials is critical. Here, we demonstrate 1D template-assisted nanowire synthesis where we observe diameter-dependent phase selectivity for tungsten phosphides. A phase bifurcation occurs to produce tungsten monophosphide and tungsten diphosphide at the cross-over nanowire diameter regime of 35–70 nm. Four-dimensional scanning transmission electron microscopy is used to identify the two phases and to map crystallographic orientations of grains at a few nm resolution. The 1D-confined phase selectivity is attributed to the minimization of the total surface energy, which depends on the nanowire diameter and chemical potentials of precursors. Theoretical calculations are carried out to construct the diameter-dependent phase diagram, which agrees with experimental observations. Our findings suggest a crystallization route to stabilize topological materials confined in 1D.

Dual residence time for droplets to coalesce with a liquid surface.

When droplets approach a liquid surface, they have a tendency to merge in order to minimize surface energy. However, under certain conditions, they can exhibit a phenomenon called coalescence delay, where they remain separate for tens of milliseconds. This duration is known as the residence time or the noncoalescence time. Surprisingly, under identical parameters and initial conditions, the residence time for water droplets is not a constant value but exhibits dual peaks in its distribution. In this paper, we present the observation of the dual residence times through rigorous statistical analysis and investigate the quantitative variations in residence time by manipulating parameters such as droplet height, radius, and viscosity. Theoretical models and physical arguments are provided to explain their effects, particularly why a large viscosity or/and a small radius is detrimental to the appearance of the longer residence time peak.

Bioinspired Plateau–Rayleigh Instability on Fibers: From Droplets Manipulation to Continuous Liquid Films

AbstractThe Plateau–Rayleigh instability (PRI) of a liquid column, which always spontaneously breaks into droplets to minimize surface energy, underlies a variety of fascinating phenomena in daily life and industrial applications. Different from the free liquid column, the evolution of the liquid film on a fiber involves solid‐liquid interfaces which allow for regulating the PRI. Recently, natural fibers with certain topologies have witnessed various dynamic liquid behaviors from droplet manipulation to continuous liquid films. Tailoring the topology of local curved liquid film by the structural‐confinement is the key to manipulating liquids, where the asymmetric Laplace pressure generated by the asymmetric/non‐spherical liquid film promotes the liquid motion. In nature, the spider silk collects droplets efficiently by the spindle‐knot structure; while the mulberry silk enables a smooth surface‐coating on dual‐parallel fibers. Drawing inspirations, many artificial structured fibers are developed to precisely regulate liquid behaviors in the form of either separated droplets or continuous liquid films, which have demonstrated applications as fluidic coating, micro‐patterning, and materials fabrication. Here, recent research progress on bioinspired fibrous PRI from the viewpoints of tailoring the Laplace pressure by rationally designing the surface topology, which offers inspiration for liquid manipulation using open fibrous media, is reviewed.

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

The multi-principal element alloynanoparticles (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 (≈100ns) 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.

Influence of degree of substitution on the hydroxypropyl-β-cyclodextrin complexation with rifampicin in water solution: a molecular simulation.

Hydroxypropyl-β-cyclodextrin (HPβCD) is one of the derivatized cyclodextrins most widely used as an excipient in the pharmaceutical industry, for its capacity to improve certain drugs properties. Different configurations of HPβCD are possible depending on the number and location of the 2-hydroxypropyl groups substituted on the glucose rings. Rifampicin has become the most commonly clinically used antibiotic against tuberculosis in recent years, despite its low solubility and variable bioavailability. Different techniques and materials have been proposed to enhance the properties of rifampicin: cyclodextrin complexation is one of them. The van der Waals term was the main contribution to the interaction energy, which then decisively conditioned the complex configurations. The size of rifampicin did not allow the whole molecule to fit into the host. Moreover, interaction energy was much greater when the guest was located near each rim of HPβCD, where rifampicin was partially included in the cavity and formed inclusion complexes. The piperazine tail of rifampicin was included inside the host in minimum energy structures and the guest was situated near the primary rim of HPβCD in most cases, although the complex configurations depended on the degree of substitution. A molecular mechanics simulation based on the GROMOS 53A6 force field was applied in this work to study the inclusion complexes formed by twelve configurations of HPβCD, with different degrees of substitution and rifampicin in water solution. We determined the penetration potential, the complex structures with minimum energies, the possibility of forming inclusion complexes other than those of minimum energies and potential energy surfaces.

THE EFFECT OF THE CHOICE OF THE STARTING MATERIAL ON THE PHASE COMPOSITION AND PHASE STABILITY OF ZRO<sub>2</sub> PARTICLES SYNTHESIZED BY THE HYDROTHERMAL METHOD

In this work, the phase composition, microstructure and phase stability of zirconium dioxide samples obtained by hydrothermal synthesis from various starting materials were investigated. It was found that when using ZrOCl2·8H2O as a starting material, zirconium dioxide particles containing monoclinic and tetragonal (cubic) phases are formed, at the same time, when using ZrO(NO3)2·2H2O as a starting material, only the monoclinic phase was identified in the samples. The CSR dimensions calculated using the Scherrer equation are in the range from 9 to 40 nm. Analysis of SEM images of experimental samples showed that nanoparticles form conglomerates with sizes of several microns. A study of the phase stability of the t, c – ZrO2 phase from temperature exposure showed that t, c – ZrO2 is a metastable phase with CSR sizes up to annealing of 10 nm. With an increase in the annealing temperature, the metastable tetragonal (cubic) phase of ZrO2 gradually transforms into a monoclinic one, due to the processes of minimizing surface energy and particle proliferation, as well as sintering conglomerates into larger monolithic particles.

Polymorphic transformations of titanium oxides contribute to economic uranium mineralization in sandstone

Abstract Sandstone-hosted uranium (U) deposits provide a significant U resource for nuclear energy worldwide. Driven by redox reactions, tetravalent uranium-bearing minerals are commonly associated with reductants (e.g., pyrite and organic matter). However, numerous observations have revealed that tetravalent uranium-bearing minerals can spatially coexist with chemically stabilized titanium oxides in sandstone-hosted U deposits, requiring a complementary mechanism to interpret these findings. We present a new model based on in situ texture, trace-element content, and titanium isotopic ratio, as well as polymorph type and related transformation for titanium oxides from the Yaojia Formation of the southwestern Songliao Basin in northeast China. Specifically, in our model, abundant nanopores were generated during the spontaneous transformation of anatase to rutile, producing a porous material for hexavalent U adsorption. Facilitated by a U-rich source rock, adsorbed U in porous titanium oxide from the lower Yaojia Formation was up to several thousand parts per million. In order to minimize surface energy, a subsequent decrease in surface area by merging small pores is inevitable. When the evolved surface area was small enough, hexavalent U would be desorbed and subsequently transformed to tetravalent U by local reductants, forming uraninite nanoparticles on the surface of U-rich rutile with relatively large pores. Our newly proposed mechanism not only contributes to a better understanding of economic U mineralization in sandstone, but also suggests that U occurred as uranium oxide instead of brannerite in sandstone-hosted U deposits, providing a nano-mineralogical perspective required for industrial processing.

Controlled formation of three-dimensional cavities during lateral epitaxial growth

Epitaxial growth is a fundamental step required to create devices for the semiconductor industry, enabling different materials to be combined in layers with precise control of strain and defect structure. Patterning the growth substrate with a mask before performing epitaxial growth offers additional degrees of freedom to engineer the structure and hence function of the semiconductor device. Here, we demonstrate that conditions exist where such epitaxial lateral overgrowth can produce complex, three-dimensional structures that incorporate cavities of deterministic size. We grow germanium on silicon substrates patterned with a dielectric mask and show that fully-enclosed cavities can be created through an unexpected self-assembly process that is controlled by surface diffusion and surface energy minimization. The result is confined cavities enclosed by single crystalline Ge, with size and position tunable through the initial mask pattern. We present a model to account for the observed cavity symmetry, pinch-off and subsequent evolution, reflecting the dominant role of surface energy. Since dielectric mask patterning and epitaxial growth are compatible with conventional device processing steps, we suggest that this mechanism provides a strategy for developing electronic and photonic functionalities.

Atomic Reconstruction of Au Thin Films through Interfacial Strains.

Interfaces play a critical thermodynamic role in the existence of multilayer systems. Due to their utility in bridging energetic and compositional differences between distinct species, the formation of interfaces inherently creates internal strain in the bulk due to the reorganization needed to accommodate such a change. We report the effect of scaling interfacial stress by deposition of different adlayers on a host thin metal film. Intrinsic property differences between host and deposited metal atoms result in varying degree of composition and energy gradient within the interface. Interfacial stress can increase defects in the host leading to (i) energy dissipation and reorganization to minimize surface energy, and (ii) increased material strength. We infer that dissipation of interfacial stress induces defect migration, hence bulk and surface atomic reconstruction as captured by the surface roughness and grain size reduction coupled with a concomitant increase in material strength.

Suppressing metal corrosion through identification of optimal crystallographic plane for Zn batteries

Direct use of metals as battery anodes could significantly boost the energy density, but suffers from limited cycling. To make the batteries more sustainable, one strategy is mitigating the propensity for metals to form random morphology during plating through orientation regulation, e.g., hexagonal Zn platelets locked horizontally by epitaxial electrodeposition or vertically aligned through Zn/electrolyte interface modulation. Current strategies center around obtaining (002) faceted deposition due to its minimum surface energy. Here, benefiting from the capability of preparing a library of faceted monocrystalline Zn anodes and controlling the orientation of Zn platelet deposits, we challenge this conventional belief. We show that while monocrystalline (002) faceted Zn electrode with horizontal epitaxy indeed promises the highest critical current density, the (100) faceted electrode with vertically aligned deposits is the most important one in suppressing Zn metal corrosion and promising the best reversibility. Such uniqueness results from the lowest electrochemical surface area of (100) faceted electrode, which intrinsically builds upon the surface atom diffusion barrier and the orientation of the pallets. These new findings based on monocrystalline anodes advance the fundamental understanding of electrodeposition process for sustainable metal batteries and provide a paradigm to explore the processing-structure-property relationships of metal electrodes.

Inorganic intumescing alkali silicate particles

New generation intumescent coatings apply self-intumescing particles to induce expansion in a controlled manner. Various studies have investigated alkali silicate-based coatings due to their inherent expansion with the release of H2O. The presented work investigated the self-intumescing concept of alkali silicates as particles. A thorough study of inorganic alkali silicate particles as potential intumescent ingredients in passive fire protection systems was carried out by applying HSDM, TGA, FTIR, XRD, and SEM. Herein, particles of lithium-, sodium-, and potassium silicates were synthesized with varying silica-to-alkali oxide molar ratios and curing humidity. Subsequently, the hydration chemistry and thermal behavior were examined. The results revealed increased expansion potential with decreasing SiO2/M2O molar ratio (M = Na, Li, or K) in the range 3.1–7.4 and increasing curing humidity in the range 35, 50, and 90% RH. Previous studies have emphasized the effect of solid-bound H2O to induce intumescence. In this study, the influence of the softening of the silicate matrix and H2O release is highlighted to allow increased expansion potential. Here, the coupling of thermal analysis with microscopy suggests an intumescence mechanism in the order of 1) initial shrinkage due to loss of free and physical bound H2O, 2) sphere formation to minimize surface energy, 3) expansion as a result of H2O evolution and viscoelastic melt formation, and 4) second shrinkage due to sintering before 5) melting. The sodium alkali silicate particles with a SiO2/M2O molar ratio of 3.4 exhibited a timely softening of the silicate matrix from about 155 °C to provide a distinct spherical particle followed by ionic H2O evolution. As a result, hereof, hollow, spherical particles with relative solid expansions of up to 550% were obtained and maintained until a second shrinkage at 650 °C with a subsequent melting at 950 °C. In comparison, the imbalance in viscoelastic melt formation and H2O release of lithium- and potassium silicate particles resulted in less expansion. Considering the expansion potential and thermal behavior of the alkali silicate particles, it is suggested as a possible, sustainable intumescence ingredient.

Rapid nucleation and optimal surface-ligand interaction stabilize wurtzite MnSe.

Non-native structures (NNS) differ in discrete translational symmetry from the bulk ground state native structure (NS). To explore the extent of deconvolution of various factors relevant to the stabilization of the wurtzite/NNS of MnSe via a heat-up method, we performed experiments using various ligands (oleic acid, oleylamine, octadecylamine, stearic acid, and octadecene), solvents (tetraethylene glycol and octadecene), and precursor salts (manganese chloride and manganese acetate). Experiments suggest that oleic acid in the presence of tetraethylene glycol and oleylamine in the presence of octadecene stabilize wurtzite/NNS. Further, density functional theory (DFT) computations explore the interaction between the functional groups in ligands and the most exposed surfaces of wurtzite/NNS and rocksalt/NS polymorphs. Computations suggest that the interactions between relevant surface facets with carboxylic acid and the double bond functional groups suppress the phase transformation from NNS to NS. In addition, the ionizability of the precursor salt also determines the rate of formation of the metal-ligand complex and the rate of nucleation. Consequently, the formation rate of the Mn-ligand complex is expected to be greater in the case of chloride salt than acetate salt because the chloride salt has higher ionizability in ethylene glycol. From the above, we conclude that the kinetics of the wurtzite/NNS to rocksalt/NS phase transformation depends mainly on two factors: (1) nucleation/growth kinetics which is controlled by the ionizability of the precursor salt, solvent, and stability of the metal-ligand complex, and (2) the activation energy barrier of the NNS to NS conversion which is controlled by surface energy minimization with the ligand.

A comparative study of a viscous froth lens in two and three dimensions

The two-dimensional (2D) viscous froth model was initially designed to capture the dynamic behavior of dry foams within a Hele–Shaw cell, characterized by two parallel covering plates separated by a small gap. However, due to its inherent 2D nature, this model does not explicitly account for the dimension across the gap. To address this limitation, we have opted for a three-dimensional (3D) version of the viscous froth model. In this 3D model, the dynamic effect is introduced through the motion of the surface Plateau borders, while the configurations of films in bulk are determined via surface energy minimization subject to specified bubble volumes and surface Plateau border locations. We use this 3D model to simulate the motion of a viscous froth lens within a straight channel. The steady states of the viscous froth lens in 3D are primarily influenced by the driving velocity-to-gap size ratio, particularly at relatively small values of this ratio. By contrast, as the ratio becomes relatively large, the gap size begins to play a significant role in influencing the behavior of the viscous froth lens in 3D. Differences are observed in the steady-state configurations of the viscous froth lens in 3D when compared to those in 2D. However, the behavior of the viscous froth lens in 2D can be better aligned with the results in 3D by treating the drag coefficient required in the 2D viscous froth model as a fitting parameter. A further quantitative analysis indicates that the drag coefficient needed in the 2D viscous froth model may not serve as a uniform parameter for the entire foam structure. Instead, it may depend on the specific location along the evolving foam films over time.

Interfacial energy as an approach to designing amphipathic surfaces during photopolymerization curing.

Photopolymerization induced phase separation (PIPS) is a platform capable of creating heterogeneous materials from initially miscible resin solutions, where both the reaction's governing thermodynamics and kinetics significantly influence the resulting phase composition and morphology. Here, PIPS is used to develop materials in a single photopolymerization step that are hydrophobic on one face and hydrophilic on the other. These two faces possess a water contact angle difference of 50°, bridged by a bulk-scale chemical gradient. The impact of the PIPS-triggering inert additive is investigated by increasing the loading of poly(methyl methacrylate) (PMMA) in an acrylonitrile/1,6-hexanediol diacrylate comonomer resin. The extent of phase separation in the sample network depends on this loading, with increasing PMMA corresponding to macroscale domains that are more chemically and mechanically distinct. A significant period between the onsets of phase separation and reaction deceleration, determined using in situ FT-IR, facilitates this enhanced phase segregation in PMMA-modified samples. Spatially directed domain formation can be further promoted using multiple interface types in the sample mold, here, glass and stainless steel. With multiple interface types, interfacial rearrangements to minimize surface energy during resin photopolymerization result in a hydrophobic face that is nitrile-rich and a hydrophilic face that is nitrile-poor (e.g., acrylate-rich). Using this strategy, patterned wettability on a single face can also be engineered. This study illustrates the capabilities of PIPS for complex surface design and in applications requiring stark differences in surface character without sharp interfaces.