Film Formation Process Research Articles

Developing Hydration Maps of Polymer Latex Film Formation Using Terahertz Time-Domain Spectroscopy.

The dynamics of the drying process of polymer latexes after casting as a wet film onto a substrate are important to track as they influence the physical and mechanical properties and performance of the dried polymer films. Current methods used to follow this drying process include gravimetric analysis, coupled with advanced techniques like GARField-NMR or optical coherence tomography. The latter two methods provide height and spatial information in the z-direction, normal to the substrate, and occasionally in the xz- or yz-planes. Terahertz time-domain spectroscopy (THz-TDS) is a welcome addition as it provides both the structural and spectroscopic information in the parallel xy-plane, filling the geometric gap. Herein, we utilize THz-TDS to study the drying and film formation process of various polymer latexes with a broad range of glass transition temperatures. We showcase the applicability of this technique in obtaining 2D parallel hydration maps of the drying dispersions, in the form of droplets, using latex-dependent calibration lines. Our findings display known phenomena arising from the drying of the colloidal dispersions.

Electrophoretic deposition of carbon-ionomer layers on proton conducting membranes.

Synthetic and natural carbons are widely used as carrier for electrodes in electrochemical applications. They need to have a controlled morphology in order to facilitate mass and charge transport, so the process of film formation is of uttermost importance. Here we show, how carbons (after proper preconditioning) can be codeposited with an ionomer by electrophoretic deposition, a method that does allow full control of deposition conditions during the process. In view of potential applications, we focus on the direct deposition on proton-conducting membranes. Ionomers and membranes applied are based on established per-fluorinated polyethylene with SO3H-terminated side chains (PFSA). Conditions for reproducible deposition are reported in terms of optimal charge on the carbon particles, field strength in the deposition cell and necessary deposition times for a given film thickness. Additionally, a horizontal cell arrangement is suggested to avoid gravitational effects.

Iron Gall Ink Revisited: Visible Light-Induced, Eosin-Mediated Acceleration of Fe2+ Oxidation in Pattern Nanoarchitectonics of Fe3+-Tannic Acid Films.

Inspired by iron gall ink (IGI), the Fe2+ ion is utilized for the continuous formation of Fe3+-tannic acid (TA) films through its in situ oxidation to the Fe3+ ion. Although several IGI-based strategies have been developed to meet different application requirements, there remains a need for the precise kinetic control for Fe2+ oxidation, along with one-step spatial controllability. This work demonstrates a visible light-induced method for oxidizing Fe2+ to Fe3+ ions, achieving the kinetic control over Fe3+-TA film formation. Photoexcitation of eosin Y leads to significantly accelerated film formation in a continuous manner, as shown by an 11-fold increase in film thickness compared with the air oxidation-based IGI method. Mechanistic studies reveal that the process is O2-dependent, and the kinetics of the film-forming process could be easily tuned by changing the light intensity or eosin Y concentration. Furthermore, the spatiotemporal controllability of the photoreaction allows for the pattern generation of Fe3+-TA complexes, proteins, and cells.

Self-Assembly of Cyclic-Bending Collagen Fibrils by Polyimide Films.

The cyclic-bending morphologies of the fibrils formed by the self-assembly of type I collagen (Col) are closely related to the mechanisms of various diseases. Therefore, studies that allow the self-assembly of Col molecules to form cyclic-bending fibrils in vitro are vitally important. In this study, we successfully achieved the cyclic-bending shapes (specifically, a regular hexagonal shape) of Col molecules by controlling the steric structures of polyimide (PI) molecular chains through the film formation process. Specifically, when a single layer of PI film was baked, the PI molecular chains within the film bent in the direction parallel to the substrate surface plane. Repeating the layering and baking processes resulted in 3D structures of the PI molecular chains, which were oriented in the direction perpendicular to the substrate surface plane. This three-dimensional bending would result from the PI molecular chain interactions between the upper and lower layers. When the Col molecules were reacted on these film surfaces, they recognized the structures of the PI molecular chains and self-assembled to form cyclic-bending Col fibrils. Especially, in PI films subjected to three cycles of layering and baking, hemicircular-shaped Col fibrils were observed to be regularly arrayed. Additionally, these regularly cyclic-bending fibrils were aligned in the uniaxial direction through a uniaxial rubbing treatment of the PI films. This successful research is significant both as a method for controlling the morphologies of Col fibrils and as a study that explores the biomedical implications of Col fibril cyclic-bending in the living body.

“Like dissolves like” enables the synergy of fluorinated additive and fluorous solvent soaking for high-performance organic solar cells

The pre-treatment and post-treatment of organic solar cells (OSCs) are two important device engineering processes that are closely associated with photovoltaic performance. Yet these two stages are independently developed to optimize the morphology and then improve the device performance, while their synergy is believed to be more productive. In this study, the fluorinated additive and fluorous solvent soaking (FSS) are simultaneously employed in OSCs, and the “like dissolves like” concept drives their synergetic role on the morphology optimization. The fluorinated additive 1,8-diiodoperfluorooctane (FDIO) could selectively enhance the packing order and crystallinity of the acceptor through forming the fluorine-induced interactions. Moreover, fluorous solvent could penetrate into the blend film and then remove the residue FDIO while further optimizing the morphology by enhancing molecular packing. By employing the synergy of FDIO additive and FSS treatment (40 °C for 30 s), a champion power conversion efficiency (PCE) of 18.64 % with the simultaneous improvements of photovoltaic parameters is achieved. This study provides a synergetic strategy by employing fluorinated additive and fluorous solvent to tune film morphology in the film-formation and post-treatment processes, respectively, consequently advancing the photovoltaic performance of OSCs.

Wafer-scale integration of two-dimensional perovskite oxides towards motion recognition

Two-dimensional semiconductors have shown great potential for the development of advanced intelligent optoelectronic systems. Among them, two-dimensional perovskite oxides with compelling optoelectronic performance have been thriving in high-performance photodetection. However, harsh synthesis and defect chemistry severely limit their overall performance and further large-scale heterogeneous integration. Here, we report the wafer-scale integration of highly oriented nanosheets by introducing a charge-assisted oriented assembly film-formation process and confirm its universality and scalability. The shallow-trap dominance induced by structural optimization endows the device with a distinguished performance balance, including high photosensitivity close to that of single nanosheet units and fast response speed. An integrated ultra-flexible 256-pixel device demonstrates the versatility of material-to-substrate integration and conformal imaging functionality. Moreover, the device achieves efficient recognition of multidirectional motion trajectories with an accuracy of over 99.8%. Our work provides prescient insights into the large-area fabrication and utilization of 2D perovskite oxides in advanced optoelectronics.

Unraveling the Formation Process of an Organic Photovoltaic Active Layer During High‐Speed Coating Via a Synergistic Concentration‐Temperature Gradient Control Strategy

AbstractThe Layer‐by‐Layer (LbL) strategy has emerged as a highly effective approach for enhancing the performance of organic photovoltaics (OPVs), notably boosting light harvesting and fill factor through spectral complementarity and morphology optimization. Crucially, the LbL processing strategy has been found to mitigate or overcome the decline in power conversion efficiency (PCE) during high‐speed blade coating. Despite these advancements, there remains a scarcity of research into the film‐formation process and the corresponding control strategies in high‐speed printing. A novel synergistic concentration‐temperature gradient control (SCTGC) strategy aimed at achieving high‐performance LbL‐type active layers at ultra‐fast coating speeds. This investigation reveals that both baseplate temperature and solution concentration exert a nonmonotonic regulatory influence on PCEs. Fine‐tuning the concentration gradient proves instrumental in balancing microfluidic competition within the wet film, thereby facilitating stable mass transport during the film formation process, and enhancing the high‐speed processability of the relevant OPV system. Additionally, the variations in crystallization kinetics under different temperatures are monitored. This work sheds light on the coating mechanism and film formation in high‐speed coating, highlighting the efficiency of the SCTGC method.

SAW-driven directional clearance of bacteria on submerged surfaces

The process of bacterial film formation on submerged surfaces commences with the attachment of bacteria to the substrate. Appropriate combinations of topology and surface chemistry have been explored to prevent biofilm anchoring at the solid–liquid interface. However, the failure to actively remove bacteria from solid surfaces within a fluid in a directional manner results in bacterial backflow onto those surfaces, thus leading to secondary contaminations. Herein, inspired by the biology broom of the ciliary beating system, we propose an active surface sweeper mechanism assisted by charged particles and surface acoustic waves (SAW) to facilitate the directional clearance of bacteria. Through the synergistic effect of charge trapping and acoustic propelling, the sweeper system demonstrates an effective inhibition of bacterial adhesion in the initial stage of biofilm formation. Utilizing SAW for twenty seconds yields a remarkable 94.8% efficiency in bacterial clearance, with antibacterial adhesion efficiency up to 92.4% and 98.8% for Escherichia coli and Staphylococcus aureus, respectively. Moreover, the accompanying theoretical force modeling offers a comprehensive mechanistic insight into the relationship between acoustic streaming and bacteria repelling. The motion analysis of bacteria-loaded particles suggests that the acoustic radiation force, rather than the Strokes force, determines the clearance direction of bacteria.

Gradual Optimization of Molecular Aggregation and Stacking Enables Over 19% Efficiency in Binary Organic Solar Cells.

Volatile solid additive is an effective and simple strategy for morphology control in organic solar cells (OSCs). The development of environmentally friendly new additives which can also be easily removed without high-temperature thermal annealing treatment is currently a trend, and the working mechanism needs to be further studied. Herein, a highly volatile and non-halogenated solid additive 1-benzothiophene (BBT) is reported to regulate molecular aggregation and stacking of active layer components. According to the film-forming kinetics process, a momentary intermediate phase is formed during spin-coating, which slows down the film-forming process and leads to more ordered molecular stacking in the solid film after introducing solid additive BBT. Subsequently, after solvent vapor annealing (SVA) further treatment, the resultant blend films exhibit a tighter and more ordered molecular stacking. Consequently, the synergistic effect of solid additive BBT and SVA treatment can effectively control morphology of active layer and improve carrier transport characteristics, thereby enhancing the performance of OSCs. Finally, in D18-Cl:N3 system, an impressive power conversion efficiency of 19.53% is achieved. The work demonstrates that the combination of highly volatile solid additives and SVA treatment is an effective morphology control strategy, guiding the development of efficient OSCs.

Study on the enhancement of device performance by the action of carbonohydrazide at the buried bottom interface of inverted mesoporous perovskite solar cells

The interface of perovskite solar cells (PSCs) significantly influences their efficiency and stability. Researchers tend to pay more attention to the upper surface of the perovskite absorber layer and conduct relatively less research on the bottom buried interface, mainly because the bottom of the perovskite film is challenging to peel off, which increases the difficulty of the characterization of the observation and analysis. Defects at the bottom interface make it more challenging to optimize the treatment than the upper surface. For inverted PSCs, the interface located in direct contact between the light absorption layer of perovskite and the hole transport layer is the buried interface. The buried interface is the direct interface for transporting charge carriers of PSCs and is also the center of non-radiative compound enrichment. The defect density is higher than the defect density of perovskite film crystal. Due to the DMSO initially left in the commonly used perovskite precursor solution during the film formation process, evaporation during the annealing and crystallization process creates vacancy holes at the bottom of the perovskite layer film. These holes and crystal boundaries tend to produce many non-radiative recombinations. These holes are also the sites of photodecomposition, leading to reduced efficiency and stability in PSCs, ultimately impacting the overall performance of PSCs. The work adds an Al2O3 mesoporous layer on top of the hole transport layer (HTL), which reduces the direct contact area between PTAA and perovskite film. In the perovskite precursor solution, we incorporate a solid additive called Carbonohydrazide (CBH), this substance replaces some of the DMSO and fills in the voids at the bottom of the perovskite film that is left when the DMSO evaporates. This process helps to reduce non-radiative recombination and photodegradation caused by the voids at the bottom of the perovskite, leading to an improvement in the efficiency and stability of the cell. The optimization of the buried bottom interface has improved the cell’s average efficiency from 17.6 % to 19.7 %, an 11.9 % increase. The aperture area of the devices in this work is 0.048 cm2, and the photoelectric conversion efficiency of our device still reaches 80.64 % of the initial efficiency after 600 h of continuous heating in a glove box with a nitrogen atmosphere, maintaining a test temperature of 60 °C.

Studying the effect of ambient temperature variations on perovskite precursor film formation using different antisolvents

This study investigates the sensitivity of two antisolvents to ambient temperature fluctuations during the fabrication of triple-cation perovskite thin films. Chlorobenzene (CB) and ethyl acetate (EA) were employed as antisolvents in the preparation of perovskite solar cells (PSCs) under identical ambient temperature variation conditions. The experimental results reveal that the quality of the perovskite films does not exhibit a consistent trend in response to ambient temperature changes depending on the antisolvent used. When CB was used as the antisolvent, the highest-performing device, produced at an ambient temperature of 18 °C, achieved a power conversion efficiency (PCE) of 19.9 %. In contrast, when EA was employed as the antisolvent, the highest-performing device was fabricated at 25 °C, reaching a PCE of 20.5 %. Furthermore, when the ambient temperature exceeded 30 °C, all films prepared with either antisolvent exhibited significant cracking, indicating that elevated temperatures adversely affect perovskite film formation. To further investigate the mechanism through which ambient temperature affects the film-forming process, antisolvents at varying temperatures were used during perovskite film preparation to simulate transient temperature increases during formation. This study reveals that the impact of ambient temperature variations on perovskite film formation does not exhibit a uniform trend but is significantly influenced by the choice of antisolvent. Moreover, this work offers valuable insights for optimizing the fabrication of high-quality perovskite thin films.

The Correlations between Microstructures and Color Properties of Nanocrystalline Cellulose: A Concise Review.

Cellulose nanocrystals (CNCs) are a green resource which can produce photonic crystal films with structural colors in evaporation-induced self-assembly; CNC photonic crystal films present unique structural colors that cannot be matched by other colored materials. Recently, the mechanisms of CNC photonic crystal films with a unique liquid crystal structure were investigated to obtain homogenous, stable, and even flexible films at a large scale. To clarify the mechanism of colorful CNC photonic crystal films, we briefly summarize the recent advances from the correlations among the preparation methods, microstructures, and color properties. We first discuss the preparation process of CNCs, aiming to realize the green application of resources. Then, the behavior of CNCs in the formation of liquid crystal phases is studied, considering the influence of the CNCs' size and shape, surface properties, and the types and concentrations of solvents. Finally, the film formation process of CNCs and the control of structural colors during the film formation are summarized, as well as the mechanisms of CNC photonic crystal films with full color. In summary, considering the above factors, obtaining reliable commercial CNC photonic crystal films requires a comprehensive consideration of the subsequent preparation processes starting from the preparation of CNCs.

Enhancing precursor stability with suitable additives to enable blade-coating of organic-inorganic hybrid perovskites at room temperature for efficient perovskite solar modules

In this study, room temperature blade coating organic-inorganic hybrid perovskite (OIHP) films with the precursors made of adding additives such as dimethyl sulfoxide (DMSO), N,N-dimethylformamide (DMF), and N-methyl-2-pyrrolidone (NMP) to the volatile solvent of 2-methoxylethanol (2-ME) were explored. Unlike NMP, DMSO and DMF interact with the perovskites to form Lewis adducts, suggesting important factors beyond the Gutmann donor number and dielectric constant, such as molecular structure, influence adduct formation. The OIHP solar cells made of the precursors with optimized amount of DMSO, DMF and NMP showed the efficiency of 16.5 %, 16.1 % and 8.3 %, respectively. After optimizing the blade-coating process for OIHP film formation by using the Taguchi's method, the optimized OIHP solar modules (active area = 25.2 cm2) achieve PCEs of 14.6 % and 14.1 % with the precursor added 20 mol% DMSO and 30 mol% DMF, respectively. Moreover, the precursor added with DMF demonstrates better storage stability than that of DMSO, achieving the best module PCE of 13.4 % fabricated from the 3-day stored DMF-added precursors, while the module fabricated from the DMSO-added precursor shows a PCE of 9.1 %.

Waterborne polyurethane with curcumin moieties for rapid responsive warnings and emergency antimicrobial action: Application in crab freshness preservation

The ideal smart food-packaging film exhibits responsive color warnings and antimicrobial properties when food metamorphism starts. However, in practical applications, these film responses are slow, usually taking several days, which is not conducive to effective antimicrobial effects. In this study, natural plant-derived curcumin was introduced into waterborne polyurethane (WPU) dispersions through two modes: free-state and end-capping. During the film-forming process, under the influence of surface tension, the capped-end curcumin migrated to the surface and further immobilized free curcumin through π-π interactions. Consequently, curcumin accumulated on the film surface, preventing flipping in moist or hydrophobic environments, in addition to acting as a color indicator for the rapid detection of crab spoilage, thus generating ammonia for a real-time response (of approximately 60 s). Simultaneously, the curcumin degraded, producing water-soluble antimicrobial curcumin-degradation products. This study significantly advances the practical application of curcumin in smart food packaging.

Colloidal Stabilizer‐Mediated Crystal Growth Regulation and Defect Healing for High‐Quality Perovskite Solar Cells

AbstractHigh‐quality perovskite (PVK) films is essential for the fabrication of efficient and stable perovskite solar cells (PSCs). However, unstable colloidal particles in PVK suspensions often hinder the formation of crystalline films with low defect densities. Herein, ethylenediaminetetraacetic acid (EDTA) as a colloidal stabilizer into lead iodide (PbI2) is introduced colloidal solutions. EDTA forms chelated complexes with Pb2+, enhancing the electrostatic repulsion and steric hindrance between colloidal particles. This stabilizes the particles and inhibits disordered motion (Brownian motion) and excessive aggregation. As a result, PbI2 films with a uniform hole distribution are formed, providing ample pathways for subsequent PVK film growth and sufficient space. During the film formation process, the replacement of molecules by formamidinium iodide (FAI) and EDTA slows down crystallization, ultimately leading to PVK films with large grain sizes and low defect density. By using this approach, champion power conversion efficiencies (PCEs) of 24.05% for FA0.97Cs0.03PbI3 PSC, 11.08% for CsPbBr3 PSC, and 25.19% for FA0.945MA0.025Cs0.03Pb(I0.975Br0.025)3 PSC are achieved. Moreover, the EDTA‐based FA0.97Cs0.03PbI3 device retains over 90% of its initial PCE after 1000 h at the maximum power point (MPP) under continuous illumination.

Structural and electrochromic property control of WO3 films through fine-tuning of film-forming parameters

Abstract Tungsten trioxide (WO3) films, extensively investigated for their remarkable electrochromic properties, have proven to be highly versatile in numerous applications. However, the challenge of achieving large-scale WO3 films with substantial dimensions and volumes remains a critical obstacle for industrial-scale production. Among the available techniques, magnetron sputtering stands out as the most efficient and straightforward method for the industrial preparation of WO3 films. In this comprehensive study, we meticulously explored the impact of various process parameters in magnetron sputtering on the film formation properties. By employing a controlled variable approach, we systematically investigated the influence of gas flow (Ar), sputtering pressure, power, and time. Our meticulous observations revealed that each parameter exerted distinct effects on the intricate film formation process. Careful analysis of the final dataset unequivocally demonstrated that when the sputtering conditions were meticulously optimized, the resulting films exhibited an extraordinary maximum transmittance change of 85% at a specific wavelength of 0.6 μm. Furthermore, these films showcased rapid coloring and bleaching response times, clocking in at an impressive 15 and 20 s, respectively, without any significant degradation even after undergoing 5,000 cycles. These groundbreaking findings provide invaluable insights into the intricate film formation process associated with magnetron-sputtered WO3.

Interfacial Assembly of Free-Standing Polymer-Phenolic Films for Antibacterial and Antiultraviolet Applications.

We report a facile interfacial assembly strategy for the preparation of flexible polyphenol-based films for antibacterial and antiultraviolet applications. The free-standing films can be instantaneously formed via spraying tannic acid (TA) at the surface of carboxymethyl chitosan (CMCS) solutions. Compared with the traditional casting-evaporation procedure on solid substrates, the liquid interfacial assembly method for the construction of free-standing films is rapid and facile, which prevents the interface separation procedure from the substrates. The thickness and mechanical properties of the films are well controlled by changing the incubation time. The low-field nuclear magnetic resonance was used to analyze the water distributions inside the films and to distinguish the cross-linked structure of CMCS-TA films with different thicknesses, revealing the dynamics of the film formation process. Importantly, the films exhibit outstanding antibacterial and antiultraviolet properties, which are promising in the applications of wound dressings. This study provides a new avenue for the assembly of flexible free-standing films with multifunctionality via a facile and low-cost fabrication process.

Composite side chain induced ordered preaggregation in liquid state for high-performance non-halogen solvent processed organic solar cells

Eco-friendly organic solar cells (OSCs) have become a promising choice for commercialization, particularly emphasizing the importance of using non-halogenated solvents. However, non-halogenated OSCs with high-performance remain limited due to the uncontrollable preaggregation behaviors of photovoltaic materials in these solvents. Here, composite side chain engineering was shown to enhance photovoltaic performance of non-halogenated solvents processed OSCs by developing two small molecular acceptors, C10ch-F and C10ch-Cl, and to study the preaggregation behavior in toluene. Through a combination of in situ absorption analyses and molecular dynamics simulations, we demonstrated that the cyclohexyl moiety at the tail of the linear chain acted as a fixative, effectively mitigating the entanglement of the amorphous long chains and prolonging the kinetics of film formation process, resulting in reinforced molecular packing with a preferential face-on orientation. With effective charge generation, transport, and collection, C10ch-Cl-based device from Tol showed an impressive PCE of 18.4 % and 19.2 % in the binary and ternary systems. Moreover, the PCE remained at 80 % of its initial value after 790 h of continuous illumination, indicating excellent photostability. The uncovered preaggregation and realized excellent performance obtained through the composite side chain strategy may allow for further synthetic advances, potentially leading to significantly improved eco-friendly OSCs.

On-Demand Picoliter-Level-Droplet Inkjet Printing for Micro Fabrication and Functional Applications.

With the advent of Internet of Things (IoTs) and wearable devices, manufacturing requirements have shifted toward miniaturization, flexibility, environmentalization, and customization. Inkjet printing, as a non-contact picoliter-level droplet printing technology, can achieve material deposition at the microscopic level, helping to achieve high resolution and high precision patterned design. Meanwhile, inkjet printing has the advantages of simple process, high printing efficiency, mask-free digital printing, and direct pattern deposition, and is gradually emerging as a promising technology to meet such new requirements. However, there is a long way to go in constructing functional materials and emerging devices due to the uncommercialized ink materials, complicated film-forming process, and geometrically/functionally mismatched interface, limiting film quality and device applications. Herein, recent developments in working mechanisms, functional ink systems, droplet ejection and flight process, droplet drying process, as well as emerging multifunctional and intelligence applications including optics, electronics, sensors, and energy storage and conversion devices is reviewed. Finally, it is also highlight some of the critical challenges and research opportunities. The review is anticipated to provide a systematic comprehension and valuable insights for inkjet printing, thereby facilitating the advancement of their emerging applications.

Highly Efficient Layer-by-Layer Organic Photovoltaics Enabled by Additive Strategy

In this work, layer-by-layer organic photovoltaics (LbL OPVs) were prepared by sequentially spin-coating PM1 and L8-BO solutions. The solvent additive 1,8-diiodooctane (DIO), which has a high boiling point, and solid additive l,3,5-trichlorobenzene (TCB), which has a high volatile, were deliberately selected to incorporate with the L8-BO solutions. The power conversion efficiency (PCE) of LbL OPVs was considerably enhanced from 17.43% to 18.50% by employing TCB as the additive, profiting by the concurrently increased short-circuit current density (JSC) of 26.74 mA cm−2 and a fill factor (FF) of 76.88%. The increased JSCs of LbL OPVs with TCB as additive were ascribed to the tilted-up absorption edge in the long wavelength range and the external quantum-efficiency spectral difference between LbL OPVs with and without TCB as an additive. The molecular arrangement of L8-BO and the PM1 domain was enhanced with TCB as an additive, which was most likely responsible for the increased charge mobilities in the layered films processed with additives. It was indicated that the dynamic film-forming process of the acceptor layers plays a vital role in achieving efficient LbL OPVs by employing additive strategy. Over 6% PCE improvement of the LbL OPVs with PM1/L8-BO as the active layers can be achieved by employing TCB as additive.