Dual Grain Refinement Effect for Pure Aluminum with the Addition of Micrometer-Sized TiB2 Particles.

The inefficiency of grain refinement processes has traditionally been attributed to the limited utilization of heterogeneous nucleation particles within master alloy systems, resulting in the formation of abundant inactive particles. This study aims to investigate the alternative influences of particles by incorporating external micrometer-sized TiB2 particles into the grain refinement process. Through a series of experiments, the refinement efficiency, grain refinement mechanism, and resultant microstructure of TiB2 particle-induced grain refinement specimens are comprehensively examined using various microscopy and analytical techniques, including polarization microscopy (OM), scanning electron microscopy (SEM), differential scanning calorimetry (DSC), and transmission electron microscopy (TEM). Our findings demonstrate a direct correlation between increased levels of TiB2 particles and enhanced grain refinement efficiency. Moreover, the microstructure analysis reveals the distribution of TiB2 particles along grain boundaries, forming a coating due to self-assembly phenomena, while regions with a lower particle content may exhibit irregular grain structures. DSC analysis further confirms reduced undercooling, indicating the occurrence of heterogeneous nucleation events. However, TEM observations suggest that heterogeneous nucleation is not significantly influenced by the growth restriction factor attributed to TiAl3 2DC compounds. The grain refinement mechanism involving TiB2 particles is elucidated to entail both heterogeneous nucleation and physical growth restriction effects. Specifically, a reduction in average grain size is attributed not only to heterogeneous nucleation but also to the physical growth restriction effect facilitated by the TiB2 particle coating. This study offers insights into leveraging particles that do not participate in heterogeneous nucleation within master alloy-based grain refinement systems.

Heterogeneous Nucleation Regulation Amends Unfavorable Crystallization Orientation and Defect Features of Antimony Selenosulfide Film for High-Efficient Planar Solar Cells.

Antimony selenosulfide (Sb2(S,Se)3) has obtained widespread concern for photovoltaic applications as a light absorber due to superior photoelectric features. Accordingly, various deposition technologies have been developed in recent years, especially hydrothermal deposition method, which has achieved a great success. However, device performances are limited with severe carrier recombination, relating to the quality of absorber and interfaces. Herein, bulk and interface defects are simultaneously suppressed by regulating heterogeneous nucleation kinetics with barium dibromide (BaBr2) introduction. In details, the Br adsorbs and dopes on the polar planes of cadmium sulfide (CdS) buffer layer, promoting the exposure of nonpolar planes of CdS, which facilitates the favorable growth of [hk1]-Sb2(S,Se)3 films possessing superior crystallinity and small interface defects. Additionally, the Se/S ratio is increased due to the replacement of S/Se by Br, causing a downshift of the Fermi levels with a benign band alignment and a shallow-level defect. Moreover, Ba2+ is located at grain boundaries by coordination with S and Se ions, passivating grain boundary defects. Consequently, the efficiency is increased from 7.70% to 10.12%. This work opens an avenue towards regulating the heterogeneous nucleation kinetics of Sb2(S,Se)3 film deposited via hydrothermal deposition approach to optimize its crystalline orientation and defect features.

Accelerated Synthesis of TS-2 Zeolite via 2D Heterogeneous Nucleation for Efficient H2O2 Production.

MEL type c is crucial for addressing energy and environmental crises, yet efficient synthesis remains a challenge due to thermodynamic and kinetic limitations. In this work, TS-2 as typical zeolite is successfully synthesized with high efficiency (12 h with 92% yield) by introducing titanate acid (TA) 2D nanosheet into a hydrothermal synthesis system. A newly defined TA/TS-2 heterostructure is precisely identified as being incorporated into the zeolite framework via a heterogeneous nucleation mechanism. Ab initio molecular dynamics simulations deeply revealed the nucleation and growth mechanisms of the TA/TS-2 heterostructure. The formation energy barrier of Ti─O─Si structural units (88 kJ mol-1) is much lower than that of Si─O─Si units (119 kJ mol-1), leading to more efficient growth of the Ti─O─Si structure. The polarized electronic properties of Ti─O─Si (negative LUMO orbital and larger polarization) further enhanced the reaction probability and stability of Ti─Si bonding. This obtained TA/TS-2 heterostructure also demonstrated superior activity for photocatalytic production of hydrogen peroxide, which can be attributed to the abundant conductive band holes and narrow bandgap. This research provides an effective strategy for using 2D nanosheets to accelerate zeolite production, as well as an in-depth molecular-level insight into the nucleation and growth processes.

Phase Transition of Cubic Ice to Hexagonal Ice during Growth and Decomposition.

Ice, one of the most enigmatic materials on Earth, exhibits diverse polymorphism, with research mainly focusing on the most commonly observed phases: hexagonal ice (Ih), cubic ice (Ic), and stacking-disordered ice (Isd). While their formation or structural changes are crucial for advancements in cloud science, climate modeling, and cryogenic technology, the molecular mechanisms driving these phenomena remain unexplored. Herein, utilizing cryogenic transmission electron microscopy, we investigate the formation of ice at two different temperatures, demonstrating a size-dependent phase shift from Ic to Isd. Furthermore, a relatively metastable cubic phase in Isd transitions to a hexagonal phase under electron beam radiation. This transition, facilitated by crystal defects, contrasts with perfect crystalline Ic, which maintains its original phase, emphasizing the importance of defects in polymorphic phase transitions. Our findings provide novel insights on phase control during the ice growth processes and polymorphic phase transitions from the cubic-to-hexagonal phases.

In Situ Visual Observation of Surface Energy-Controlled Heterogeneous Nucleation of Metal Nanocrystals.

Electrochemical growth of metal nanocrystals is pivotal for material synthesis, processing, and resource recovery. Understanding the heterogeneous interface between electrolyte and electrode is crucial for nanocrystal nucleation, but the influence of this interaction is still poorly understood. This study employs advanced in situ measurements to investigate the heterogeneous nucleation of metals on solid surfaces. By observing the copper nanocrystal electrodeposition, an interphase interaction-induced nucleation mechanism highly dependent on substrate surface energy is uncovered. It shows that a high-energy (HE) electrode tended to form a polycrystalline structure, while a low-energy (LE) electrode induced a monocrystalline structure. Raman and electrochemical characterizations confirmed that HE interface enhances the interphase interaction, reducing the nucleation barrier for the sturdy nanostructures. This leads to a 30.92-52.21% reduction in the crystal layer thickness and a 19.18-31.78% increase in the charge transfer capability, promoting the formation of a uniform and compact film. The structural compactness of the early nucleated crystals enhances the deposit stability for long-duration electrodeposition. This research not only inspires comprehension of physicochemical processes correlated with heterogeneous nucleation, but also paves a new avenue for high-quality synthesis and efficient recovery of metallic nanomaterials.

Adhesion-Controlled Heterogeneous Nucleation of Tin Halide Perovskites for Eco-Friendly Indoor Photovoltaics.

The rapid development of the Internet of Things (IoT) has accelerated the advancement of indoor photovoltaics (IPVs) that directly power wireless IoT devices. The interest in lead-free perovskites for IPVs stems from their similar optoelectronic properties to high-performance lead halide perovskites, but without concerns about toxic lead leakage in indoor environments. However, currently prevalent lead-free perovskite IPVs, especially tin halide perovskites (THPs), still exhibit inferior performance, arising from their uncontrollable crystallization. Here, a novel adhesive bonding strategy is proposed for precisely regulating heterogeneous nucleation kinetics of THPs by introducing alkali metal fluorides. These ionic adhesives boost the work of adhesion at the buried interface between substrates and perovskite film, subsequently reducing the contact angle and energy barrier for heterogeneous nucleation, resulting in high-quality THP films. The resulting THP solar cells achieve an efficiency of 20.12% under indoor illumination at 1000 lux, exceeding all types of lead-free perovskite IPVs and successfully powering radio frequency identification-based sensors.

From adsorption to crystallization of proteins: Evidence for interface-assisted nucleation.

Protein crystallization is among the key processes in biomolecular research, but the underlying mechanisms are still elusive. Here, we address the role of inevitable interfaces for the nucleation process. Quartz crystal microbalance with dissipation monitoring (QCM-D) with simultaneously optical microscopy, confocal microscopy, and grazing-incidence small angle X-rays scattering (GISAXS) were employed to investigate the temporal behavior from the initial stage of protein adsorption to crystallization. Here we studied the crystallization of the Human Serum Albumin (HSA), the most abundant blood protein, in the presence of a charged surface and a trivalent salt. We found evidence for interface-assisted nucleation of crystals. The kinetic stages involved are initial adsorption followed by enhanced adsorption after longer times, subsequent nucleation, and finally crystal growth. The results highlight the importance of interfaces for protein phase behavior and in particular for nucleation.

Centrifugation-Mediated Crystal Growth of Attractive Colloids for Band Edge Lasing.

Attractive depletion interactions are utilized to organize colloidal particles into crystalline arrays with high crystallinity through spontaneous phase separation. However, uncontrolled nucleation frequently leads to the formation of crystalline grains with varied crystal orientations, which hampers the optical performance of photonic crystals. Here, colloidal crystals have been engineered with uniform orientation and high surface coverage by applying centrifugal force during the depletion-induced assembly of polystyrene particles. The centrifugal force encourages the particles to move toward the bottom surface, which fosters heterogeneous nucleation and supports rapid crystal growth, yielding densely-packed and uniformly-arranged crystal grains with high reflectivity. This study has observed that the nucleation and crystal growth behavior is significantly influenced by the salt concentration. Based on the pair potentials, the transition boundary has been quantitatively analyzed between fluid and crystal phases and identified the threshold for homogeneous nucleation. Utilizing the high-reflectivity colloidal crystals, band-edge lasing is achieved by dissolving the water-soluble dye into the aqueous suspensions. Upon optical excitation, a lasing emission characterized is observed by a narrow spectral width at the short-wavelength band edge. Notably, the laser wavelength can be adjusted by altering the salt concentration or particle diameter, offering a versatile approach to tuning the optical properties.

Exploiting intermediate wetting on superhydrophobic surfaces for efficient icing prevention.

HYPOTHESIS: Superhydrophobic surfaces can effectively prevent the freezing of supercooled droplets in technological systems. Droplets on superhydrophobic surfaces commonly not only wet the top asperities (Cassie State), but also partially penetrate into microstructure due to surface properties, environment, and droplet impact occurring in real-world applications. Implications on ice nucleation can be expected and are little explored. It remains elusive how anti-icing surfaces can be designed to exploit intermediate wetting phenomena. EXPERIMENTS: We utilized engineered micro-/nanostructures, specifically micropillars, to modulate the wetting fraction in the microstructure. The behavior of intermediate wetting with supercooling and resulting implications on ice nucleation delay when potential nucleation sites are formed in the microcavities were investigated using experimental, theoretical, and simulation components. FINDINGS: The temperature-dependent wetting fraction in the microstructure increased at supercooled temperatures, partly activated by condensation in the microcavities. At -10/-20 °C, a critical wetting fraction led to maximum ice nucleation delays, with experimental results consistent with theoretical predictions. This critical wetting fraction minimized the effective contact area solid-to-liquid along the partially wetted microstructure. The study establishes physical relations between ice nucleation delays, geometrical surface parameters and wettability properties in the intermediate wetting regime, providing guidance for the design of ice resistant microstructured surfaces.

Stabilizing Zn/electrolyte Interphasial Chemistry by a Sustained-Release Drug Inspired Indium-Chelated Resin Protective Layer for High-Areal-Capacity Zn//V2O5 Batteries.

For zinc-metal batteries, the instable chemistry at Zn/electrolyte interphasial region results in severe hydrogen evolution reaction (HER) and dendrite growth, significantly impairing Zn anode reversibility. Moreover, an often-overlooked aspect is this instability can be further exacerbated by the interaction with dissolved cathode species in full batteries. Here, inspired by sustained-release drug technology, an indium-chelated resin protective layer (Chelex-In), incorporating a sustained-release mechanism for indium, is developed on Zn surface, stabilizing the anode/electrolyte interphase to ensure reversible Zn plating/stripping performance throughout the entire lifespan of Zn//V2O5 batteries. The sustained-release indium onto Zn electrode promotes a persistent anticatalytic effect against HER and fosters uniform heterogeneous Zn nucleation. Meanwhile, on the electrolyte side, the residual resin matrix with immobilized iminodiacetates anions can also repel detrimental anions (SO4 2- and polyoxovanadate ions dissolved from V2O5 cathode) outside the electric double layer. This dual synergetic regulation on both electrode and electrolyte sides culminates a more stable interphasial environment, effectively enhancing Zn anode reversibility in practical high-areal-capacity full battery systems. Consequently, the bio-inspired Chelex-In protective layer enables an ultralong lifespan of Zn anode over 2800 h, which is also successfully demonstrated in ultrahigh areal capacity Zn//V2O5 full batteries (4.79 mAh cm-2).

Generalized Synthesis of Highly-Dispersed, Ultrafine Transition Metal Nanoparticles on Silica Spheres for Enhanced Optical Absorption.

Robust synthesis of ultrafine metal nanoparticles (ufMNPs) below 5 nm with clean surfaces and strong optical absorption in the visible spectral range is challenging due to their instability originating from large surface-to-volume ratios. This work reports a general strategy involving two sequential steps: i) loading metal precursor ions onto the surface of silica nanospheres (SiOx NSs) by forming a uniform coating of metal oxyhydroxide [MOy(OH)z] through preferred surface acid-base reactions and ii) thermally reducing MOy(OH)z in forming gas at elevated temperatures to form ufMNPs evenly dispersed on the surface of SiOx NSs. The capability of this synthesis strategy is verified by loading ufMNPs of various transition metals and bimetallic combinations onto the SiOx NSs. The ufMNPs exhibit strong optical absorption enhanced by the optical scattering resonances in the SiOx NSs, which generate intense electric fields near the surface of the SiOx NSs. The SiOx NSs also support stabilizing the ufMNPs, which do not need additional organic capping reagents. The successful synthesis of SiOx-NS-supported ufMNPs with clean surfaces and enhanced optical absorption is promising for exploring the photocatalytic properties of ufMNPs.

Composition templating for heterogeneous nucleation of intermetallic compounds.

Refinement of intermetallic compounds (IMCs) through enhancing heterogeneous nucleation during casting process is an important approach to improve the properties of aluminium alloys, which greatly increases the economy value of recycled Al-alloys. However, heterogeneous nucleation of IMCs is inherently more difficult than that of a pure metal or a solid solution. It requires not only creation of a crystal structure but also the positioning of 2 or more different types of atoms in the lattice with specific composition close to that of the nucleated IMCs. Previous understanding on heterogeneous nucleation is based on structural templating, usually considering the small lattice misfit at the interface between the nucleating solid and substrate. In this work, we proposed a hypothesis and demonstrated that composition templating plays a critical role in heterogeneous nucleation of IMCs. The experimental results revealed that segregation of Fe atoms on the AlB2 surface, i.e., the Fe modified AlB2 particle, provides the required composition templating and hence enhances heterogeneous nucleation of α-Al15(Fe, Mn)3Si2, resulting in a significant refinement of the α-Al15(Fe, Mn)3Si2 particles in an Al-5 Mg-2Si-1.0Mn-1.2Fe alloy.

Performance Enhancement of Three-Dimensional MAPbI3 Perovskite Solar Cells by Doping Perovskite Films with CsPbX3 Quantum Dots.

Perovskite thin films directly impact solar cell properties, making defect reduction crucial in perovskite solar cell research. In our study, we used perovskite quantum dots in the anti-solvent to act as nucleation centers in MAPbI3 thin films. These centers had lower nucleation barriers than homogeneous nucleation, improving perovskite crystallinity, reducing defects, and extending carrier lifetime. Fine-tuning the energy band also enhanced carrier transport. The most effective results were obtained using CsPb(Br0.5 I0.5)3 perovskite quantum dots. The resulting device, ITO/SnO2/MAPbI3 (300 nm)/spiro-OMeTAD (200 nm)/Ag (100 nm), achieved a 12.88% power conversion efficiency, a 16% increase from the standard element. The modified device maintained approximately 95% of its efficiency over 100 h in a 70% humidity environment.

Photochemical Shield Enabling Highly Efficient Perovskite Photovoltaics.

Oxygen is difficult to be physically removed. Oxygen will be excited by light to form free radicals which further attack the lattice of perovskite. The stabilization of α-FAPbI3 against δ-FAPbI3 is the key to optimize perovskite solar cells. Herein, the simple molecule, benzaldehyde (BAH) is adopted. The photochemical shield will be established in perovskite layer. Moreover, heterogeneous nucleation induced by BAH enhances the crystallization of α-FAPbI3. Consequently, the stability of device is improved significantly. The target device maintains 95% of original power conversion efficiency after 1500 h under air conditions and light-emitting diode light. The power conversion efficiency increases from 23.21% of pristine device to 24.82% of target device.

In Situ Formation of 2D Perovskite Seeding for Record-Efficiency Indoor Perovskite Photovoltaic Devices.

With 40% efficiency under room light intensity, perovskite solar cells (PSCs) will be promising power supplies for low-light applications, particularly for Internet of Things (IoT) devices and indoor electronics, shall they become commercialized. Herein, ß-alaninamide hydrochloride (AHC) is utilized to spontaneously form a layer of 2D perovskite nucleation seeds for improved film uniformity, crystallization quality, and solar cell performance. It is found that the AHC addition indeed improves film quality as demonstrated by better uniformity, lower trap density, smaller lattice stress, and, as a result, a 10-fold increase in charge carrier lifetime. Consequently, not only does the small-area (0.09 cm2 ) PSCs achieve a power conversion efficiency of 42.12%, the large-area cells (1.00 cm2 , and 2.56 cm2 ) attain efficiency as high as 40.93%, and 40.07% respectively. All of these are the highest efficiency values for indoor photovoltaic cells with similar sizes, and more importantly, they represent the smallest efficiency loss due to area scale-up. This work provides a new method to fabricate high-performance indoor PSCs (i-PSCs) for IoT devices with great potential in large-area printing technology.

Regioselective Growth of Colloidal Crystals Induced by Depletion Attraction.

Colloidal crystals display photonic stopbands that generate reflective structural colors. While micropatterning offers significant value for various applications, the resolution is somewhat limited for conventional top-down approaches. In this work, a simple, single-step bottom-up approach is introduced to produce photonic micropatterns through depletion-mediated regioselective growth of colloidal crystals. Lithographically-featured micropatterns with planar surfaces and nano-needle arrays as substrates are employed. Heterogeneous nucleation is drastically suppressed on nano-needle arrays due to minimal particle-to-needles overlap of excluded volumes, while it is promoted on planar surfaces with large particle-to-plane volume overlap, enabling regioselective growth of colloidal crystals. This strategy allows high-resolution micropatterning of colloidal photonic crystals, with a minimum feature size as small as 10 µm. Stopband positions, or structural colors, are controllable through concentration and depletant and salt, as well as particle size. Notably, secondary colors can be created through structural color mixing by simultaneously crystallizing two different particle sizes into their own crystal grains, resulting in two distinct reflectance peaks at controlled wavelengths. The simple and highly reproducible method for regioselective colloidal crystallization provides a general route for designing elaborate photonic micropatterns suitable for various applications.

Perovskite Crystallization Regulation via Antimonene Quantum Sheets for Highly Efficient and Stable Solar Cells.

The two-step deposition method offers significant advantages in the production of high-performance planar perovskite solar cells (PSCs). Nevertheless, there are still numerous challenges in regulating perovskite crystallization during the two-step process. In this work, two-dimensional (2D) material antimonene quantum sheets (AMQSs) as an additive are introduced to regulate the crystallization process of perovskite. As a result, perovskite films with high crystalline quality and vertical growth orientation are obtained by AMQSs providing heterogeneous nucleation sites with the penetration of a mixture solution of AMQSs and FAI into the PbI2 layer. Also, the influence mechanism of AMQSs on the crystallization of perovskite film is analyzed in details. At the same time, due to the chemical interaction between antimonene and the uncoordinated Pb2+, the defects in the perovskite are efficiently passivated. In addition, the energy level at the perovskite/SnO2 interface becomes more matched, leading to improved charge transport and extraction with the incorporation of AMQSs. Benefiting from the versatile AMQSs, the power conversion efficiency (PCE) of PSCs made by PbI2 + FAI:AMQSs is improved from 20.65 to 22.31% with the vastly enhanced Jsc and Voc. The ambient and operational stability of the unencapsulated PSCs fabricated using the PbI2 + FAI:AMQSs method were significantly improved, retaining 80% of the original PCE after being stored in a dark environment at a relative humidity of 30-40% for 18 days and 83% of the original PCE following continuous AM 1.5G illumination for 200 h.

The smallest nanodrop describable via macroscopic interfacial concepts: Testing classical heterogeneous nucleation theory with perfect wetting down to 3 nm.

HYPOTHESIS: The smallest nanodrop tractable with macroscopic notions such as the interfacial energy could be determined by comparing heterogeneous nucleation observations and capillary theory predictions at decreasing drop diameters dp. ANALYSIS: This is done here for the condensation of n-butanol vapors on polyethylene glycol nano-globules (3 nm ≤ dp ≤ 9 nm). We use published activation probability measurements P(w,dp), where w is the accurately controlled saturation ratio of n-butanol vapor in a gas stream exiting a saturator. The maximal saturation ratio achieved in the nucleation region by cooling this gas-vapor stream in the apparatus of Gallar et al. satisfies Smax = Cw. The key unknown constant C and the preexponential term K governing the nucleation rate are determined by assuming that classical theory applies to the largest particles used. This yields P(Smax,dp) data, directly comparable with capillary theory with perfect wetting. FINDINGS: Excellent agreement is found above 5 nm for the critical dependence Smax(dp) resulting from the constraint P(Smax,dp) = 0.5. The entire P(Smax,dp) curves also agree closely between 5 and 7 nm. Smaller particles depart only slightly from theory, even at dp = 3 nm. Capillary theory hence describes accurately the heterogeneous nucleation process above 3-5 nm, provides a reliable method to determine Smax, and yields experimentally the nucleation rate constant K.

Role of WSOCs and pH on Ammonium Nitrate Aerosol Efflorescence: Insights into Secondary Aerosol Formation.

Efflorescence of ammonium nitrate (AN) aerosols significantly impacts atmospheric secondary aerosol formation, climate, and human health. We investigated the effect of representative water-soluble organic compounds (WSOCs) (sucralose (SUC), glycerol (GLY), and citric acid (CA) on AN:WSOC aerosol efflorescence using vacuum Fourier transform infrared spectroscopy. Combining efflorescence relative humidity (ERH) measurements, heterogeneous nucleation rates, and model predictions, we found that aerosol viscosity, correlating with molecular diffusion, effectively predicted ERH variations among the AN:WSOC aerosols. WSOCs with higher viscosity (SUC and CA) hindered efflorescence, while GLY with a lower viscosity showed a minor effect. At a low AN:CA molar ratio (10:1), CA promoted ERH, likely due to CA crystallization. Increasing the droplet pH inhibited AN:CA aerosol efflorescence. In contrast, for AN:SUC and AN:GLY aerosols, efflorescence is pH-insensitive. With the addition of trivial sulfate, AN:SUC droplets exhibited two-stage efflorescence, coinciding with ammonium sulfate and AN efflorescence. Given the atmospheric abundance, the morphology, phase, and mixing state of nitrate aerosols are significant for atmospheric chemistry and physics. Our results suggest that AN:WSOCs aerosols can exist in the amorphous phase in the atmosphere, with efflorescence behavior depending on the aerosol composition, viscosity, pH, and the cation and anion interactions in a complex manner.

Microstructure and Strength of Ti-6Al-4V Samples Additively Manufactured with TiC Heterogeneous Nucleation Site Particles.

Our research aims to investigate the fabrication of additively manufactured (AMed) Ti-6Al-4V samples under reduced power with the addition of TiC heterogeneous nucleation site particles. For this aim, Ti-6Al-4V samples are fabricated with and without TiC heterogeneous nucleation site particles using an EOS M 290 machine under optimal parameters and reduced power conditions. The microstructure and tensile behavior of the produced samples were studied. In addition, a single-track test was performed to obtain a good understanding of the suppression of gas pores and balling formation with the addition of TiC heterogeneous nucleation site particles. It was found that the formation of gas pores and balling was suppressed with the addition of heterogeneous nucleation site particles within the metallic powder.