Showing papers on "Crystallization published in 2020"

Crystallization in Confinement

Abstract: Many crystallization processes of great importance, including frost heave, biomineralization, the synthesis of nanomaterials, and scale formation, occur in small volumes rather than bulk solution Here, the influence of confinement on crystallization processes is described, drawing together information from fields as diverse as bioinspired mineralization, templating, pharmaceuticals, colloidal crystallization, and geochemistry Experiments are principally conducted within confining systems that offer well-defined environments, varying from droplets in microfluidic devices, to cylindrical pores in filtration membranes, to nanoporous glasses and carbon nanotubes Dramatic effects are observed, including a stabilization of metastable polymorphs, a depression of freezing points, and the formation of crystals with preferred orientations, modified morphologies, and even structures not seen in bulk Confinement is also shown to influence crystallization processes over length scales ranging from the atomic to hundreds of micrometers, and to originate from a wide range of mechanisms The development of an enhanced understanding of the influence of confinement on crystal nucleation and growth will not only provide superior insight into crystallization processes in many real-world environments, but will also enable this phenomenon to be used to control crystallization in applications including nanomaterial synthesis, heavy metal remediation, and the prevention of weathering

Isothermally crystallized perovskites at room-temperature

Abstract: The solution processability of photoactive halide perovskites differentiates them from traditional inorganic semiconducting materials that require multiple post-processing steps such as thermal/vacuum/blowing- and solvent-assisted treatment. Here we report a technical breakthrough of isothermally crystallizing high-quality perovskite films at room-temperature (RT) without the necessity of any post-processing. This process takes advantage of our discovery of a metastable intermediate of lower-dimensionality formed by amine-assisted crystallographic lattice expansion from an initial three-dimensional perovskite. Using in situ optoelectrical/chemical and ex situ structural characterizations, a detailed understanding of the low-dimensional metastable intermediate is developed. In conjunction with the metastable intermediate, the rapid evaporation of the solvent and amine facilitates ultra-fast crystallization at RT within seconds. This RT rapidly synthesized perovskite film exhibits a carrier diffusion length of 2.9 μm and {00} preferred orientation with an ultrahigh Lotgering factor of 97%. These films are highly compatible to conventional or inverted devices, demonstrating 22.3% and 23.1% power conversion efficiencies, respectively.

Kinetic pathways of crystallization at the nanoscale

Abstract: Nucleation and growth are universally important in systems from the atomic to the micrometre scale as they dictate structural and functional attributes of crystals. However, at the nanoscale, the pathways towards crystallization have been largely unexplored owing to the challenge of resolving the motion of individual building blocks in a liquid medium. Here we address this gap by directly imaging the full transition of dispersed gold nanoprisms to a superlattice at the single-particle level. We utilize liquid-phase transmission electron microscopy at low dose rates to control nanoparticle interactions without affecting their motions. Combining particle tracking with Monte Carlo simulations, we reveal that positional ordering of the superlattice emerges from orientational disorder. This method allows us to measure parameters such as line tension and phase coordinates, charting the nonclassical nucleation pathway involving a dense, amorphous intermediate. We demonstrate the versatility of our approach via crystallization of different nanoparticles, pointing the way to more general applications.

Room-temperature liquid diffused separation induced crystallization for high-quality perovskite single crystals.

Abstract: Large single crystals serve as an ideal platform for investigating intrinsic material properties and optoelectronic applications. Here we develop a method, namely, room-temperature liquid diffused separation induced crystallization that uses silicone oil to separate the solvent from the perovskite precursors, to grow high-quality perovskite single crystals. The growth kinetics of perovskite single crystals using this method is elucidated, and their structural and optoelectronic properties are carefully characterized. The resultant perovskite single crystals, taking CH3NH3PbBr3 as an example, exhibit approximately 1 µs lifetime, a low trap density of 4.4 × 109 cm−3, and high yield of 92%, which are appealing for visible light or X-ray detection. We hope our findings will be of great significance for the continued advancement of high-quality perovskite single crystals, through a better understanding of growth mechanisms and their deployment in various optoelectronics. The diffused separation induced crystallization strategy presents a major step forward for advancing the field on perovskite single crystals. Perovskites are appealing for optoelectronics, but high-quality perovskite single crystals should be grown at low temperature to minimize trap density. Here, the authors report a room-temperature liquid-diffused-induced crystallization for growth of high-quality hybrid perovskite single crystals.

Arylazopyrazoles for Long-Term Thermal Energy Storage and Optically Triggered Heat Release below 0 °C.

Abstract: Arylazopyrazole derivatives based on four core structures (4pzMe, 3pzH, 4pzH, and 4pzH-F2) and functionalized with a dodecanoate group were demonstrated to store thermal energy in their metastable Z isomer liquid phase and release the energy by optically triggered crystallization at -30 °C for the first time. Three heat storage-release schemes were discovered involving different activation methods (optical, thermal, or combined) for generating liquid-state Z isomers capable of storing thermal energy. Visible light irradiation induced the selective crystallization of the liquid phase via Z-to-E isomerization, and the latent heat stored in the liquid Z isomers was preserved for longer than 2 weeks unless optically triggered. Up to 92 kJ/mol of thermal energy was stored in the compounds, demonstrating remarkable thermal stability of Z isomers at high temperatures and liquid-phase stability at temperatures below 0 °C.

Multi-cation perovskites prevent carrier reflection from grain surfaces.

Abstract: The composition of perovskite has been optimized combinatorially such that it often contains six components (AxByC1−x−yPbXzY3−z) in state-of-art perovskite solar cells. Questions remain regarding the precise role of each component, and the lack of a mechanistic explanation limits the practical exploration of the large and growing chemical space. Here, aided by transient photoluminescence microscopy, we find that, in perovskite single crystals, carrier diffusivity is in fact independent of composition. In polycrystalline thin films, the different compositions play a crucial role in carrier diffusion. We report that methylammonium (MA)-based films show a high carrier diffusivity of 0.047 cm2 s−1, while MA-free mixed caesium-formamidinium (CsFA) films exhibit an order of magnitude lower diffusivity. Elemental composition studies show that CsFA grains display a graded composition. This curtails electron diffusion in these films, as seen in both vertical carrier transport and surface potential studies. Incorporation of MA leads to a uniform grain core-to-edge composition, giving rise to a diffusivity of 0.034 cm2 s−1 in CsMAFA films. A model that invokes competing crystallization processes allows us to account for this finding, and suggests further strategies to achieve homogeneous crystallization for the benefit of perovskite optoelectronics. Methylammonium is shown to influence the crystallization process in hybrid lead halide perovskites, leading to a more homogeneous chemical distribution of caesium and formamidinium and improved charge transport between grains in multi-cation systems.

Regulated Crystallization of Efficient and Stable Tin-Based Perovskite Solar Cells via a Self-Sealing Polymer

Abstract: Tin-based perovskite solar cells (PVSCs) have emerged as the most promising lead-free perovskite materials owing to their superior optoelectronic properties. However, the deficiency of accurate con...

Mechanism of Crystal Formation in Ruddlesden–Popper Sn-Based Perovskites

Abstract: Knowledge of the mechanism of formation, orientation, and location of phases inside thin perovskite films is essential to optimize their optoelectronic properties. Among the most promising, low toxicity, lead-free perovskites, the tin-based ones are receiving much attention. Here, an extensive in situ and ex situ structural study is performed on the mechanism of crystallization from solution of 3D formamidinium tin iodide (FASnI(3)), 2D phenylethylammonium tin iodide (PEA(2)SnI(4)), and hybrid PEA(2)FA(n)(-1)Sn(n)I(3)(n)(+1) Ruddlesden-Popper perovskites. Addition of small amounts of low-dimensional component promotes oriented 3D-like crystallite growth in the top part of the film, together with an aligned quasi-2D bottom-rich phase. The sporadic bulk nucleation occurring in the pure 3D system is negligible in the pure 2D and in the hybrid systems with sufficiently high PEA content, where only surface crystallization occurs. Moreover, tin-based perovskites form through a direct conversion of a disordered precursor phase without forming ordered solvated intermediates and thus without the need of thermal annealing steps. The findings are used to explain the device performances over a wide range of composition and shed light onto the mechanism of the formation of one of the most promising Sn-based perovskites, providing opportunities to further improve the performances of these interesting Pb-free materials.

Black phosphorus quantum dots in inorganic perovskite thin films for efficient photovoltaic application.

Abstract: Black phosphorus quantum dots (BPQDs) are proposed as effective seed-like sites to modulate the nucleation and growth of CsPbI2Br perovskite crystalline thin layers, allowing an enhanced crystallization and remarkable morphological improvement. We reveal that the lone-pair electrons of BPQDs can induce strong binding between molecules of the CsPbI2Br precursor solution and phosphorus atoms stemming from the concomitant reduction in coulombic repulsion. The four-phase transition during the annealing process yields an α-phase CsPbI2Br stabilized by BPQDs. The BPQDS/CsPbI2Br core-shell structure concomitantly reinforces a stable CsPbI2Br crystallite and suppresses the oxidation of BPQDs. Consequently, a power conversion efficiency of 15.47% can be achieved for 0.7 wt % BPQDs embedded in CsPbI2Br film-based devices, with an enhanced cell stability, under ambient conditions. Our finding is a decisive step in the exploration of crystallization and phase stability that can lead to the realization of efficient and stable inorganic perovskite solar cells.

Ligand Orientation-Induced Lattice Robustness forHighly Efficient and Stable Tin-Based Perovskite Solar Cells

Abstract: Low-toxicity tin-based perovskites have exhibited huge potential for photovoltaics applications. However, the facile oxidation of Sn2+ to Sn4+ induces ubiquitous Sn vacancies and p-type doping in p...

Colloidal crystal engineering with metal–organic framework nanoparticles and DNA

Abstract: Colloidal crystal engineering with nucleic acid-modified nanoparticles is a powerful way for preparing 3D superlattices, which may be useful in many areas, including catalysis, sensing, and photonics. To date, the building blocks studied have been primarily based upon metals, metal oxides, chalcogenide semiconductors, and proteins. Here, we show that metal–organic framework nanoparticles (MOF NPs) densely functionalized with oligonucleotides can be programmed to crystallize into a diverse set of superlattices with well-defined crystal symmetries and compositions. Electron microscopy and small-angle X-ray scattering characterization confirm the formation of single-component MOF superlattices, binary MOF–Au single crystals, and two-dimensional MOF nanorod assemblies. Importantly, DNA-modified porphyrinic MOF nanorods (PCN-222) were assembled into 2D superlattices and found to be catalytically active for the photooxidation of 2-chloroethyl ethyl sulfide (CEES, a chemical warfare simulant of mustard gas). Taken together, these new materials and methods provide access to colloidal crystals that incorporate particles with the well-established designer properties of MOFs and, therefore, increase the scope of possibilities for colloidal crystal engineering with DNA. Colloidal crystals assembled from nanoscale building blocks are powerful designer materials with diverse functionalities. Here, the authors describe a colloidal crystal engineering strategy to prepare hierarchical structures from metal–organic framework nanoparticles and DNA which retain permanent porosity and catalytic activity.

Shape-preserving amorphous-to-crystalline transformation of CaCO3 revealed by in situ TEM

Abstract: Organisms use inorganic ions and macromolecules to regulate crystallization from amorphous precursors, endowing natural biominerals with complex morphologies and enhanced properties. The mechanisms by which modifiers enable these shape-preserving transformations are poorly understood. We used in situ liquid-phase transmission electron microscopy to follow the evolution from amorphous calcium carbonate to calcite in the presence of additives. A combination of contrast analysis and infrared spectroscopy shows that Mg ions, which are widely present in seawater and biological fluids, alter the transformation pathway in a concentration-dependent manner. The ions bring excess (structural) water into the amorphous bulk so that a direct transformation is triggered by dehydration in the absence of morphological changes. Molecular dynamics simulations suggest Mg-incorporated water induces structural fluctuations, allowing transformation without the need to nucleate a separate crystal. Thus, the obtained calcite retains the original morphology of the amorphous state, biomimetically achieving the morphological control of crystals seen in biominerals.

Systematic investigation of the growth kinetics of β-Ga2O3 epilayer by plasma enhanced chemical vapor deposition

Abstract: β-Ga2O3 has attracted much attention due to its ultrawide-bandgap (∼4.9 eV) with a high breakdown field (8 MV/cm) and good thermal/chemical stability. In order for β-Ga2O3 to be used in electronic and optoelectronic devices, epitaxial growth technology of thin films should be given priority. However, challenges are associated with the trade-off growth rate with crystallization and surface roughness in conventional epitaxy. Herein, plasma enhanced chemical vapor deposition was used to grow the β-Ga2O3 epilayer, and the growth kinetics process has been systematically investigated. A high growth rate of ∼0.58 μm/h and a single 2 ¯ 01 plane orientation with a full width at half maximum value of 0.86° were obtained when grown on the c-plane sapphire substrate at the growth temperature of 820 °C. Then, a proposed model for the mechanism of nucleation and growth of β-Ga2O3 epitaxial films is established to understand the precursor transport and gas phase reaction process. This work provides a cheap, green, and efficient epitaxial growth method, which is indispensable for device applications of β-Ga2O3.

Ionic solids from common colloids

Abstract: From rock salt to nanoparticle superlattices, complex structure can emerge from simple building blocks that attract each other through Coulombic forces1–4. On the micrometre scale, however, colloids in water defy the intuitively simple idea of forming crystals from oppositely charged partners, instead forming non-equilibrium structures such as clusters and gels5–7. Although various systems have been engineered to grow binary crystals8–11, native surface charge in aqueous conditions has not been used to assemble crystalline materials. Here we form ionic colloidal crystals in water through an approach that we refer to as polymer-attenuated Coulombic self-assembly. The key to crystallization is the use of a neutral polymer to keep particles separated by well defined distances, allowing us to tune the attractive overlap of electrical double layers, directing particles to disperse, crystallize or become permanently fixed on demand. The nucleation and growth of macroscopic single crystals is demonstrated by using the Debye screening length to fine-tune assembly. Using a variety of colloidal particles and commercial polymers, ionic colloidal crystals isostructural to caesium chloride, sodium chloride, aluminium diboride and K4C60 are selected according to particle size ratios. Once fixed by simply diluting out solution salts, crystals are pulled out of the water for further manipulation, demonstrating an accurate translation from solution-phase assembly to dried solid structures. In contrast to other assembly approaches, in which particles must be carefully engineered to encode binding information12–18, polymer-attenuated Coulombic self-assembly enables conventional colloids to be used as model colloidal ions, primed for crystallization. Oppositely charged colloidal particles are assembled in water through an approach that allows electrostatic interactions to be precisely tuned to generate macroscopic single crystals.

Crystallization by particle attachment is a colloidal assembly process.

Abstract: The nucleation of crystals has long been thought to occur through the stochastic association of ions, atoms or molecules to form critical nuclei, which will later grow out to crystals1. Only in the past decade has the awareness grown that crystallization can also proceed through the assembly of different types of building blocks2,3, including amorphous precursors4, primary particles5, prenucleation species6,7, dense liquid droplets8,9 or nanocrystals10. However, the forces that control these alternative pathways are still poorly understood. Here, we investigate the crystallization of magnetite (Fe3O4) through the formation and aggregation of primary particles and show that both the thermodynamics and the kinetics of the process can be described in terms of colloidal assembly. This model allows predicting the average crystal size at a given initial Fe concentration, thereby opening the way to the design of crystals with predefined sizes and properties.

K+-induced crystallization of polymeric carbon nitride to boost its photocatalytic activity for H2 evolution and hydrogenation of alkenes

Abstract: Crystalline semiconductors with ordered long-range structure and minimized phase defect are capable of efficient separation and diffusion of photoexcited charge carriers, which is crucial for achieving high photocatalytic performances. Here, we present a new strategy using KCl as structure inducer, where potassium ions (K+) act as a smart “binder” for re-ordering the structure of amorphous polymer carbon nitride (PCN) to furnish K+ implanted crystalline PCN (KPCN). The X-ray photoelectron spectroscopy depth profiling with Ar+ cluster ion sputtering illustrated that the element K is uniformly distributed in bulk of KPCN. The microstructure evolution of KPCN under elevated temperature was identified using in situ Fourier-transform infrared spectroscopy. This crystalline structure endows the ordered electronic transmission channels in KPCN, thus enhanced the efficiency of hot charge carriers separation and migration, as well as visible light capture. Therefore, the re-ordered KPCN displays nearly 20 times enhancement toward photocatalytic hydrogen evolution, and high activity in water-splitting-based alkenes hydrogenation using the in-situ photo-generated H-species from water as sustainable H-source. The present work highlights a green and reliable strategy to remodel the structure of PCN by K+ thus dramatically boosting the photocatalytic activity for hydrogen evolution as well as water-splitting-based photosynthesis of high value-added fine chemicals.

Migration Crystallization Device Based on Biomass Photothermal Materials for Efficient Salt-Rejection Solar Steam Generation

Abstract: Solar-driven interfacial water evaporation has attracted increasing interest because of its high photothermal conversion efficiency. However, a big challenge still remains as salt crystallization i...

Solid-State Dewetting Dynamics of Amorphous Ge Thin Films on Silicon Dioxide Substrates.

Abstract: We report on the dewetting process, in a high vacuum environment, of amorphous Ge thin films on SiO2/Si (001). A detailed insight of the dewetting is obtained by in situ reflection high-energy electron diffraction and ex situ scanning electron microscopy. These characterizations show that the amorphous Ge films dewet into Ge crystalline nano-islands with dynamics dominated by crystallization of the amorphous material into crystalline nano-seeds and material transport at Ge islands. Surface energy minimization determines the dewetting process of crystalline Ge and controls the final stages of the process. At very high temperatures, coarsening of the island size distribution is observed.

Balancing the pre-aggregation and crystallization kinetics enables high efficiency slot-die coated organic solar cells with reduced non-radiative recombination losses

Abstract: Slot-die coating being compatible with the roll-to-roll technique has been regarded as a promising tool for upscaling the manufacturing of organic solar cells (OSCs). However, there has been a significant gap between the efficiencies of the state-of-the-art spin-coated devices and the scalable processed devices. The active layer morphology is crucial to achieve high efficiency in OSCs, which depends on the conditions of film fabrication. To figure out and optimize the slot-die coating process, a deeper understanding of the film formation kinetics is important. Herein, in situ measurements of the slot-die coating process based on the PM7:IT4F system are demonstrated to illustrate the aggregation and crystallization evolution at various die temperatures and substrate temperatures. OSCs with a high power conversion efficiency of 13.2% are achieved at 60 °C die temperature/60 °C substrate temperature due to the improved exciton dissociation, charge transport and suppressed non-radiative charge recombination. The optimized morphology is attributed to the balanced polymer pre-aggregation and small molecule crystallization kinetics. The unsuitable die temperature leads to overlarge phase separation and consequently inefficient exciton dissociation while the improper substrate temperature results in weak crystallization and the following shrunken carrier lifetime with strong non-radiative combination. This work provides fundamental understanding on the correlations among processing methodology, solution pre-aggregation, morphology formation kinetics, device physics and device performance and affords guidance for device optimization in scalable manufacturing.

Congruent Release of Drug and Polymer from Amorphous Solid Dispersions: Insights into the Role of Drug-Polymer Hydrogen Bonding, Surface Crystallization, and Glass Transition.

Abstract: Drug loading is an important parameter known to impact the release rate of a poorly soluble drug from an amorphous solid dispersion (ASD). Recent studies have shown that small increases in drug loading can dramatically reduce the drug release rate from ASDs prepared with poly(vinylpyrrolidone-co-vinyl acetate) (PVPVA). However, the link between drug physicochemical properties and the drug loading where the release is abruptly compromised is not well understood. This study probes the role of different factors on the relative dissolution rates of drug and polymer from PVPVA-based ASDs as a function of drug loading: (1) the impact of drug-polymer hydrogen bonding interactions on the initial dissolution rate of ASDs, investigated using two structural analogues, indomethacin (IND) and indomethacin methyl ester (INDester), (2) the influence of surface drug crystallization, observed for INDester ASDs, and (3) by changing temperature, the impact of the "wet" glass transition temperature (Tg). Scanning electron microscopy (SEM), with or without energy dispersive X-ray (EDX) analysis, Fourier transform infrared spectroscopy (FTIR), and powder X-ray diffraction (PXRD) were utilized to study the solid-state phase behavior and/or drug enrichment on the partially dissolved ASD tablet surfaces. Nanoparticle tracking analysis (NTA) was utilized to study the solution-state phase behavior. It was found that, contrary to expectations, ASDs with drug-polymer hydrogen bonding exhibited poorer initial release at moderate drug loadings (15-25%) as compared to the non-hydrogen bonding analogue ASDs. Surface crystallization led to the deterioration of dissolution performance. Lastly, Tg relative to experimental temperatures also appeared to play a role in the observed dissolution behavior as a function of drug loading. These findings shed light on potential mechanisms governing ASD dissolution performance and will aid in the development of optimized ASD formulations with enhanced dissolution performance.

Superionic Halogen-Rich Li-Argyrodites Using In Situ Nanocrystal Nucleation and Rapid Crystal Growth.

Abstract: Although several crystalline materials have been developed as Li-ion conductors for use as solid electrolytes in all-solid-state batteries (ASSBs), producing materials with high Li-ion conductivities is time-consuming and cost-intensive. Herein, we introduce a superionic halogen-rich Li-argyrodite (HRLA) and demonstrate its innovative synthesis using ultimate-energy mechanical alloying (UMA) and rapid thermal annealing (RTA). UMA with a 49 G-force milling energy provides a one-pot process that includes mixing, glassification, and crystallization, to produce as-milled HRLA powder that is ∼70% crystallized; subsequent RTA using an infrared lamp increases this crystallinity to ∼82% within 25 min. Surprisingly, this HRLA exhibits the highest Li-ion conductivity among Li-argyrodites (10.2 mS cm-1 at 25 °C, cold-pressed powder compact) reported so far. Furthermore, we confirm that this superionic HRLA works well as a promising solid electrolyte without a decreased intrinsic electrochemical window in various electrode configurations and delivers impressive cell performance (114.2 mAh g-1 at 0.5 C).

Gradient transition zone structure in “steel–copper” sample produced by double wire-feed electron beam additive manufacturing

Abstract: This paper describes the results of an investigation into a microstructure formation on a wire-feed electron beam additive manufactured “steel–copper” bimetallic sample. The peculiarities of a gradient zone structure with a smooth change of components’ concentration are revealed. The heterogeneity of copper and steel distribution in the gradient zone is provided by copper solidification and precipitation mechanisms. Both solidification of coarse copper inclusions in the interdendrite areas or along the dendrite boundaries and precipitation of fine Cu-based particles at the cooling stage from the solid solution of Cu in γ-Fe are the main factors of structure formation during the double wire gradient zone deposition. The presence of such fine copper precipitates from the supersaturated solid solution was revealed by means of transmission electron microscopy. The shape of copper particles in the gradient zone varies from spherical to oblong and irregular. The shape of steel particles and/or grains is mainly determined by the peculiarities of the crystallization zone and is characterized by the primary crystallization of γ-iron dendrites from the liquid melt. A physical scheme describing a variation in phase composition and microstructure in gradient zone of the bimetallic specimen was proposed.