Crystal Nucleation Process Research Articles

Phase behavior and crystal nucleation of hard triangular prisms.

The interplay between densification and positional ordering during the process of crystal nucleation is a greatly investigated topic. Even for the simplest colloidal model-hard spheres-there has been much debate regarding the potential foreshadowing of nucleation by significant fluctuations in either local density or local structure. Considering anisotropic particles instead of spheres adds a third degree of freedom to the self-organization process of crystal nucleation: orientational ordering. Here, we investigate the crystal nucleation of hard triangular prisms. Using Monte Carlo simulations, we first carefully determine the crystal-fluid coexistence values and calculate the nucleation barriers for two degrees of supersaturation. Next, we use brute force simulations to obtain a large set of spontaneous nucleation events. By studying the time evolution of the local density, positional ordering, and orientational ordering in the region in which the nucleus first arises, we demonstrate that all local order parameters increase simultaneously from the very start of the nucleation process. We thus conclude that we observe no precursor for the crystal nucleation of hard triangular prisms.

Effects of structure similar additive on the crystallization of L-phenylalanine from aqueous solution

A comprehensive understanding of the effect of structure similar additives on the nucleation and growth of amino acid in aqueous solution is of great significance for the crystallization of L-phenylalanine and industrial production of anhydrous L-phenylalanine. This paper mainly focuses on the influence of L-tyrosine on the crystallization process of L-phenylalanine by investigating the variation and typical phenomenon in solubility, metastable zone width, crystal nucleation and growth process, and crystal morphology. The results show that the existence of L-tyrosine can obviously increase the solubility and narrow the metastable zone of L-phenylalanine thus promote the nucleation process. Meanwhile, L-tyrosine can also selectively inhibit the formation of monohydrate and improve the purity of industry-favored anhydrous L-phenylalanine in the final product. In order to explore the inhibiting effect of L-tyrosine in crystallization process, the molecular configurations in two different crystallization states were simulated by using Molecular Dynamics.The results show that water and L-phenylalanine molecules tend to form anhydrous crystals when the addition proportion of L-tyrosine increases. The theoretical calculations are in good agreement with the experimental data. The conclusions of this paper will provide new ideas and effective controlling approaches for L-phenylalanine crystals’ morphology and amino acids’ crystallization process.

Morphological regulation of Pt/CeO2 and its catalytic dehydrogenation of methylcyclohexane in fixed bed reactor

A series of Pt/CeO2 compounds with hollow spheres (Pt/CeO2–S), wires (Pt/CeO2–W), and particle (Pt/CeO2–P) morphologies were prepared and further used for catalytic liquid organic hydrogen carrier (LOHC) dehydrogenation. The exposure and distribution of different crystal faces affected the nucleation process of crystals and then formed different microscopic morphologies. Compared with Pt/CeO2–W and Pt/CeO2–P, Pt/CeO2–S showed hollow spherical structures with significantly higher oxygen vacancy concentrations and specific surface areas. These structural differences not only affected platinum (Pt) dispersion, but also affected the activity and stability of the catalyst, thus promoting methylcyclohexane (MCH) conversion. The fixed bed reaction showed that Pt/CeO2–S had excellent catalytic activity, with the MCH conversion rate at 97.7 % and hydrogen release rate of 350.50 mmol/g(Pt)/min, and it still maintained stable activity after 72 h. Under the same conditions, the MCH conversion rates for Pt/CeO2–W and Pt/CeO2–P were only 77.23 % and 32.02 %, respectively. Therefore, through the growth pattern and morphology controls of catalyst supports, this was an effective means for improving the dehydrogenation performance of LOHC.

Preparation of UiO-66 membrane through heterogeneous nucleation assisted growth strategy for efficient CO2 capture under humid conditions

Metal-organic frameworks (MOFs) have driven the development of polycrystalline membranes in the field of gas separation owing to the strong adsorption-desorption behavior and stable framework structure. However, the poor heterogeneous bonding ability between crystals and the substrate leads to the unsatisfactory gas separation as well as low stability of MOF membranes, especially in the humid environment. Herein, we prepared a thin and defect-free UiO-66 membrane by a crystal heterogeneous nucleation assisted growth strategy for efficient CO2/N2 separation. The addition of small amount of water in the precursor solution promoted the crystal nucleation process on the substrate surface. Meanwhile, the smooth PDMS interlayer guaranteed the heterogeneous well-intergrown of crystals into thin UiO-66 membranes, and provided a hydrophobic environment. Therefore, the dense UiO-66 membrane with a small thickness exhibited a high CO2 permeance (177.4 × 10−9 mol·m−2·s−1·Pa−1) with moderate CO2/N2 selectivity (24.3) under humid conditions. Furthermore, the prepared membrane demonstrated excellent renewable performance after dehumidification at high temperature, and maintained good hydrothermal stability during long-term operation under the humid environment. This work provides a new insight for the design of high-quality MOF membranes and promotes the development of MOF membranes in practical gas separation process.

Efficient and Highly Stable Lateral Perovskite Single‐Crystal Solar Cells through Crystal Engineering and Weak Ion Migration

AbstractThe lateral device structure for perovskite solar cells (PSCs) has garnered significant attention, primarily due to its elimination of the need for expensive transparent electrodes. However, the performance of lateral devices, which are more sensitive to crystal quality and charge carrier transport bottlenecks, has lagged far behind the predominant vertical PSCs. Herein, by modulating the crystal nucleation and growth processes of thin FA0.75MA0.25PbI3 (FA = formamidinium; and MA = methylammonium) single crystals, crystal quality and carrier transport are improved, resulting in a power conversion efficiency (PCE) of 12.64%, a record for lateral PSCs. Investigation of the device's stability reveals that iodide ion migration is suppressed due to a reduction in the iodide vacancy concentration combined with weak interface iodide ion migration. It is shown that the latter effect is a result of the perpendicular direction of the ion migration and the electric field in the lateral PSCs. Consequently, these lateral single‐crystal PSCs display remarkable operational stability, retaining 100% of their initial PCE after 1200 h of steady‐state output at the maximum power point voltage (Vmpp) under 1 sun illumination. This work highlights the advantages of lateral single‐crystal devices and their potential to address key ion migration issues of PSCs.

Improving Hybrid Tin Halide Films by Tin Trifluoromethanesulfonate for Lead-Free Perovskite Solar Cells.

Tin-based perovskite solar cells (Sn-PSCs) without toxic lead ions outperform other types of lead-free PSCs in terms of photovoltaic performance. To avoid the oxidation of Sn2+ cations and the formation of vacancy defects, most reports involve the addition of SnF2 to the perovskite precursor solution, but hybrid tin halide (Sn-PVK) films still suffer from poor crystallinity and stability. In this work, we used an alternative additive of tin trifluoromethanesulfonate (Sn(OTF)2). Compared to SnF2, the solubility of Sn(OTF)2 in the precursor solution is greatly improved, and the crystal nucleation process is delayed, resulting in the enhancement of crystal growth. The coordination ability of the OTF- anions suppresses the oxidation of Sn2+ cations, which promotes the stability of Sn-PVK films. By replacing the conventional additive of SnF2 with Sn(OTF)2, the device achieves an increase in power conversion efficiency from 7.96% to 10.3%, while the stability of the devices is improved simultaneously.

The impact of crystal phase transition on the hardness and structure of kidney stones

Calcium oxalate kidney stones, the most prevalent type of kidney stones, undergo a multi-step process of crystal nucleation, growth, aggregation, and secondary transition. The secondary transition has been rather overlooked, and thus, the effects on the disease and the underlying mechanism remain unclear. Here, we show, by periodic micro-CT images of human kidney stones in an ex vivo incubation experiment, that the growth of porous aggregates of calcium oxalate dihydrate (COD) crystals triggers the hardening of the kidney stones that causes difficulty in lithotripsy of kidney stone disease in the secondary transition. This hardening was caused by the internal nucleation and growth of precise calcium oxalate monohydrate (COM) crystals from isolated urine in which the calcium oxalate concentrations decreased by the growth of COD in closed grain boundaries of COD aggregate kidney stones. Reducing the calcium oxalate concentrations in urine is regarded as a typical approach for avoiding the recurrence. However, our results revealed that the decrease of the concentrations in closed microenvironments conversely promotes the transition of the COD aggregates into hard COM aggregates. We anticipate that the suppression of the secondary transition has the potential to manage the deterioration of kidney stone disease.

Hydration mechanism and photocatalytic antibacterial performance of cement-based composites modified by hydrophilic nano-TiO2 particles

In this paper, the hydration process of cement paste with hydrophilic nano-TiO2 particles was studied by microcalorimeter and electrochemical impedance spectroscopy, and the hydration mechanism was explored based on Krstulovic-Dabic kinetic model. Meanwhile, the photocatalytic activity and antibacterial properties of TiO2-modified cement pastes were investigated by ultraviolet spectrophotometer and enzyme activity analyzer respectively. The results show that TiO2 nanoparticles can promote the hydration rate of cement in the acceleration stage, increase the cumulative heat release of early hydration, but delay the hydration process in the later stage. The Krstulovic-Dabic model can effectively simulate the hydration process of cement pastes with TiO2. Nano-TiO2 helps to increase the hydration rate of the crystal nucleation and growth process (NG) and shorten the duration of phase boundary reaction process (I), but has a negative impact on ion diffusion process (D). The functional relationship between the resistivity ρ of TiO2 cement-based composites and the hydration kinetic parameters was established: ρ(t)=−1k1ln[β1+t50t−t0].The degree of hydration of cement can be assessed by electrochemical in-situ non-destructive monitoring of the sample. In addition, the photocatalytic oxidation rate of TiO2-modified cement-based composites was up to 69.4%. Compared with the control sample without nano TiO2, the antibacterial ability was increased by 72.35%. In this paper, nano-TiO2 was applied to cement system, which provided a new idea for the preparation and application of photocatalytic antibacterial cement-based composites.

Using brewing waste diatomite activated by ball milling to simple and sustainable synthesis of nano-H-ZSM-5 aggregates

Brewing waste diatomite (BSDT) from the beer industry is a highly productive silica-aluminate solid waste and realizing the resource utilization of BSDT is the key to achieving the circular economy. Synthesis of zeolites from BSDT is a high value-added utilization method, but using BSDT to synthesize zeolites via “silica-alumina homologation” is difficult because of its high SiO2/Al2O3 ratio and low chemical activity. Further, using BSDT to synthesize high-quality nano-zeolites on a large scale through a simple and green method is a huge challenge. In this study, we propose a facile and scalable strategy to utilize BSDT as the only Si-Al source to prepare high-quality nano-H-ZSM-5 aggregates with hierarchical structures in a single templating agent system by solid-like transformations. The activation of BSDT was achieved by mechanical ball milling. Crystallite size and hierarchical structures are controlled by decoupling the crystal nucleation and growth processes. Due to the “silica-alumina homologation” system, aluminum species enter the zeolite framework along with the dynamic crystallization process and provide uniform acidic sites. In the methanol conversion reaction, the obtained catalysts showed longer lifetime (172.5 h) and higher light olefin selectivity (62.5%) compared to commercial catalysts. This strategy is simple, economical, and scalable, and can be extended to the synthesis of other framework-type zeolites with high SiO2/Al2O3 ratios.

Online In Situ Real-Time Experimental Investigation of the Crystallization Characteristics and Kinetic Models during the Nucleation and Growth Process of Para-Xylene Suspension Crystallization

Online In Situ Real-Time Experimental Investigation of the Crystallization Characteristics and Kinetic Models during the Nucleation and Growth Process of Para-Xylene Suspension Crystallization

Recovery of sulphur dioxide by converter dust synergistic coke decomposition of phosphogypsum

To further improve the decomposition ratio and sulfur dioxide mass yield of coke-reduced solid waste phosphogypsum (PG), converter dust (CD) is proposed as a novel additive. The effects of raw material ratio, time and temperature for roasting on the decomposition process of PG were inspected by simulation calculations and fluidized bed experiments. It turns out that the optimized reaction conditions are Fe3O4/Ca of 0.6, C/Ca of 0.4 at 1100 °C for 24 min, under which the PG decomposition ratio and SO2 mass yield are 99.56 % and 97.64 %, respectively. The addition of CD is able to reduce the initial reaction temperature from 975 °C to 914 °C, and promote the release of SO2. Kinetic analysis shows the mechanistic equation for this process is obtained as G(α) = [−ln(1 − α)]3/2, indicating that the decomposition reaction mechanism is a crystal nucleation and growth-controlled process. The chemical mechanism of the process is that coke and Fe3O4 in the CD convert CaSO4 to the intermediate CaS, and Fe3O4 is oxidized to Fe2O3. Then CaS and CaSO4 continue to react with Fe2O3 to form Ca2Fe2O5 and SO2. The presence of Fe2O3 accelerations the rate of CaS and CaSO4 roasting reaction and lowers the reaction temperature. Meanwhile, the self-decomposition of PG also produces CaO and SO2. Finally, a process for SO2 recovery from CD synergized with coke decomposition of PG is proposed.

Recent Theoretical Advancement of Boron-Rich Compounds for Applications in High-Density Energy Conversion Devices

Boron-rich compounds (IBCs) such as boron suboxide (B6O) and boron subphosphide (B12P2) are derived from the α-rhombohedral boron lattice with extreme hardness and unusual electrical properties. These compounds display an extraordinary self-healing ability to repair the lattice defects generated from exposure to high-energy irradiation. This unique ability will enable these boron-rich compounds to be deployed in nuclear battery devices for space or deep-sea exploration applications when coupled with their high hole mobility.Synthesis and control of the stoichiometry of IBCs are the key technical challenge. For instance, the electrical properties of B6O are susceptible to specific B:O ratios. Thus far, the highest quality B6O crystals were obtained from high-pressure, high-temperature (HP-HT) experiments using mixed boron and boron oxide powders. Nevertheless, a mature synthesis protocol yielding consistent, high-quality B6O crystals has not been established.In this talk, density functional theory (DFT) was used to understand how the structural, electronic, and thermodynamic stabilities of B6O (and other IBCs) are influenced by the interstitial elements and point defects at the icosahedral sites. Using the hybrid HSE functional, we confirmed that the perfect B6O bulk is a p-type semiconductor with a direct band gap of 2.8 eV. Furthermore, by screening the α-boron compounds systematically, we found that a simple octet rule may offer a consistent explanation for the variations in the computed electronic structures. Then, the thermodynamic calculations based on the DFT method predict that formations of interstitial defects become favorable only at higher temperatures.To understand the self-healing property, the nudged elastic band (NEB) method was employed to identify the minimum energy pathways for the diffusions of dislocated B and O atoms. The diffusion of icosahedral B atoms has an energy barrier of 0.16 eV, confirming that the boron vacancies can be repaired with little kinetic limitation. Nevertheless, a substantially perturbed lattice requires more complex structural reorganization and thus incurs higher barriers (> 1 eV).Lastly, reactive molecular dynamics simulations with a frozen core were performed to gain insights into the initial crystal nucleation process using a newly developed ReaxFF force field. For the first time, we can gain a molecular perspective on the formations of the boron icosahedra (B12) motif and the energetic profile. Such knowledge will aid the experimental design of IBC synthesis.

Effects of Structural Relaxation of Glass-Forming Melts on the Overall Crystallization Kinetics in Cooling and Heating.

In the theoretical treatment of crystallization, it is commonly assumed that the relaxation processes of a liquid proceed quickly as compared to crystal nucleation and growth processes. Actually, it is supposed that a liquid is always located in the metastable state corresponding to the current values of pressure and temperature. However, near and below the glass transition temperature, Tg, this condition is commonly not fulfilled. In such cases, in the treatment of crystallization, deviations in the state of the liquid from the respective metastable equilibrium state have to be accounted for when determining the kinetic coefficients governing the crystallization kinetics, the thermodynamic driving force of crystallization, and the surface tension of the aggregates of the newly evolving crystal phase including the surface tension of critical clusters considerably affecting the crystal nucleation rate. These factors may greatly influence the course of the overall crystallization process. A theoretical analysis of the resulting effects is given in the present paper by numerical solutions of the J(ohnson)-M(ehl)-A(vrami)-K(olmogorov) equation employed as the tool to model the overall crystallization kinetics and by analytical estimates of the crystallization peak temperatures in terms of the dependence on cooling and heating rates. The results are shown to be in good agreement with the experimental data. Possible extensions of the theory are anticipated and will be explored in future analysis.

Prediction of the phase diagram of liquid–liquid phase separation during crystallization via a molecular mechanism study

Oiling-out is a unique liquid–liquid phase separation phenomenon in solution crystallization. The unknown microscopic mechanism of oiling-out makes it difficult to control and significantly reduces the separation efficiency. In this work, an adsorption–desorption mechanism of temperature-driven molecular clustering is proposed based on the configuration search and the transformation process monitoring of dimers. This mechanism indicates that the stable and sufficient solute dimers in the solvent is the key condition for inducing oiling-out, accompanied by the transformation among various dimer configurations. Based on this mechanism, a prediction method of oiling-out phase diagram has been established through configurational stability analysis and determination of the total energy-temperature curve. This prediction method has been successfully applied to five systems: pyraclostrobin, vanillin, ethyl vanillin, citric acid, and benzoic acid. Importantly, the purity of pyraclostrobin is increased from 42.76% to 99.32% with the assistance of the oiling-out phase diagram. These findings not only provide advanced insights into understanding and controlling oiling-out during crystallization, but also highlight the role that oiling-out plays in the molecular assembly process of crystal nucleation.

The role of solute conformation, solvent–solute and solute–solute interactions in crystal nucleation

AbstractThe induction time for nucleation can differ based on the solutions used to conduct a crystallization, which can in turn impact the efficiency and economics of a crystallization process, the crystal size distribution, the morphology and ultimately functionality of the final product. Establishing a link between the nucleation pathway/solution structure and nucleation induction time is essential to achieve improved comprehension of the process of crystal nucleation from solution. In this study, the role of solute conformation, solvent–solute interaction, and solute–solute interaction in nucleation was examined using tolbutamide as a model compound in toluene and toluene–alcohol solutions. Through a combination of induction time experiments, attenuated total reflection Fourier transformed infrared spectroscopy, nuclear magnetic resonance spectroscopy, molecular dynamics simulations, and quantum chemical calculations, it was found that not only solvent–solute interactions but also solute–solute interactions and structural similarities between molecular self‐assemblies in the solution and synthons in the crystal structure, can significantly influence the nucleation induction time.

The Crystallization of Disordered Materials under Shock Is Governed by Their Network Topology.

When the shock load is applied, materials experience incredibly high temperature and pressure conditions on picosecond timescales, usually accompanied by remarkable physical or chemical phenomena. Understanding the underlying physics that governs the kinetics of shocked materials is of great importance for both physics and materials science. Here, combining experiment and large-scale molecular dynamics simulation, the ultrafast nanoscale crystal nucleation process in shocked soda-lime silicate glass is investigated. By adopting topological constraints theory, this study finds that the propensity of nucleation is governed by the connectivity of the atomic network. The densification of local networks, which appears once the crystal starts to grow, results in the underconstrained shell around the crystal and prevents further crystallization. These results shed light on the nanoscale crystallization mechanism of shocked materials from the viewpoint of topological constraint theory.

Crystallization discrepancies in Mg65Zn30Ca5 metallic glass ribbon and thin film revealed by nanocalorimetry

In this study, ribbons and thin films of Mg65Zn30Ca5 (at.%) metallic glass were prepared by melt-spinning and magnetron sputtering deposition techniques, respectively. With nanocalorimetry and structural characterization, the rapid crystallization mechanisms of the Mg65Zn30Ca5 ribbon and thin film were evaluated comparatively. The metallic glass thin film has a lower crystallization temperature but a higher apparent activation energy compared to the ribbon. The granular and hierarchical surface of the film promotes heterogeneous nucleation, leading to a lower crystallization temperature. The crystal nucleation and growth processes are analyzed using the Johnson-Mehl-Avrami equation. Compared with the ribbon, whose crystallization is dominated by the growth of pre-existing nuclei, both nucleation and crystal growth occur during the crystallization of the thin film, leading to a higher activation energy. With respect to the ribbon, the crystal growth rate of the thin film is exceptionally higher because of the formation of ordered microstructures inside the film.

Hydration and microstructure of ternary high-ferrite Portland cement blends incorporating a large amount of limestone powder and fly ash

This paper studied the mechanical properties, hydration process, and microstructure of ternary high-ferrite Portland cement (HFC) blends with replacement at levels up to 50 % with limestone powder (LP) and fly ash (FA). Two mechanisms, synergy and negative effects between LP and FA are observed in ternary HFC-LP-FA blends. The synergistic effects between LP and FA in ternary HFC blends mainly exhibit improving flexural strengths, improving compressive strengths before 28 days, decreasing drying shrinkage and cumulative heat, accelerating the crystal nucleation and growth process (NG), stabilizing the ettringite (AFt) phase, prolonging polymerization of alumino-silicate chains, and refining the pore size distribution, etc. However, the synergistic effect between LP and FA in ternary HFC blends cannot compensate for the dilution effect caused by a large amount of LP and FA replacement. The adverse effects between LP and FA in ternary HFC blends are emerged and mainly exhibited decreasing in compressive strengths after 28 days and increasing total porosity percentages. LP plays a predominant role at an early age (before 28 days) in HFC blends and increases the cumulative heat; Specifically the cumulative heat of LP25 (25 indicates percentage replacement of HFC) before 10 h is 2.2 J/g higher compared to HFC. In addition, a rapid increase of bound water is emerged from 3 days to 28 days, for instance the bound water content in LP25 increases by 55.9 % from 3 days to 28 days. It is attributed to the nucleation effect of LP providing more nucleation sites and accelerating NG process. LP in HFC blends leads to the formation of monocarbonate and AFt phase trends to stabilization. FA plays a predominant role at the later hydration age (from 28 days to 90 days) in HFC blends attributing its pozzolanic reaction. Furthermore, the synergistic effects between FA and LP in ternary HFC blends are mainly occurred at a later age.

Impact of Crystal Nuclei on Dissolution of Amorphous Drugs.

Amorphous drugs are used to improve bioavailability of poorly water-soluble drugs. Crystallization must be managed to take full advantage of this formulation strategy. Crystallization of amorphous drugs proceeds in a sequence of crystal nucleation and growth, with different kinetics. At low temperatures, crystal nucleation is fast, but crystal growth is slow. Therefore, amorphous drugs may generate dense but nanoscale crystal nuclei. Such tiny nuclei cannot be detected using routine powder X-ray diffraction (PXRD) and polarized light microscopy (PLM). However, they may negate the dissolution advantage of amorphous drugs. In this work, for the first time, the impact of crystal nuclei on dissolution of amorphous drugs was studied by monitoring the real-time dissolution from amorphous drug films, with and without crystal nuclei, and the evolving crystallinity in the films. Three model drugs (ritonavir/RTV, posaconazole/POS, and nifedipine/NIF) were chosen to represent different crystallization tendencies in the supercooled liquid state, namely, slow-nucleation-and-slow-growth (SN-SG), fast-nucleation-and-slow-growth (FN-SG), and fast-nucleation-and-fast-growth (FN-FG), respectively. We find that although the amorphous films containing nuclei do not show obvious differences from the nuclei-free films under PLM and PXRD before dissolution, they have inferior dissolution performance relative to the nuclei-free amorphous films. For SN-SG drug RTV, crystal nuclei have negligible impact on the crystallization of amorphous films, dissolution rate, and supersaturation achieved. However, they cause earlier de-supersaturation by inducing crystallization in solution as heterogeneous seeds. For FN-SG drug POS and FN-FG drug NIF, crystal nuclei accelerate crystallization in the amorphous films leading to lower supersaturation achieved with POS, and elimination of any supersaturation with NIF. Dissolution profiles of amorphous films can be further analyzed using a derivative function of the apparent dissolution rate, which yields amorphous solubility, initial intrinsic dissolution rate, and onset of crystallization in the amorphous films. This study highlights that although crystal nuclei are undetectable with routine analytical methods, they can significantly negate, or even eliminate, the dissolution advantage of amorphous drugs. Hence, understanding crystal nucleation process and developing approaches to prevent it are necessary to fully realize the benefits of amorphous solids.

Humidity-Insensitive, Large-Area-Applicable, Hot-Air-Assisted Ambient Fabrication of 2D Perovskite Solar Cells.

2D layered perovskites (LPs) have shown great potential to deliver high-performance photovoltaic devices with long-term stability. Despite many signs of progress being made in film quality and device performance, LP films are mainly processed in strict conditions and through non-scalable techniques. Here, the hot-air-assisted ambient fabrication technique is introduced to prepare LP films for efficient and stable solar cells. The high-quality LP films with good crystallinity, preferable orientation and desirable morphology are obtained by balancing the crystal nucleation and growth processes. Employing the synchrotron-based in situ grazing-incidence X-ray diffraction technique, hot air induces the solidification of solutes and forms an intermediate at the air-liquid interface, which transforms into 3D-like perovskite, followed by the growth of the 2D species toward the substrate. The optimal LP film delivers a device power conversion efficiency of 16.36%, the best value for the LP-based solar cells prepared by the non-spin-coating techniques. The solar cell performance is insensitive to the film processing humidity and the device size is upscalable, which promises real-world deployment of LP-based optoelectronic devices.