Fabrication Of Films Research Articles

Influence of substrate edge chamfer geometric features on the edge effect of spin-coating film

Abstract The spin-coating method is a widely employed technique for thin film fabrication. However, edge effects can adversely affect the quality and utility of the films produced. This study investigates the influence of chamfered edges on the substrate during the spin-coating process on edge effects. Both experimental and simulation results indicate that smaller chamfer angles contribute to reducing the width of edge effects. Conversely, the width of the chamfer has a relatively minor impact on the extent of edge effects.

Luminescence enhancement behavior of KSr1.96Sm0.04Nb5O15/PVDF composite thick film after electric polarization

A novel composite thick film exhibiting luminescent enhancement behavior was prepared using Sm3+ doped KSr2Nb5O15 ferroelectric microcrystals and polyvinylidene difluoride (PVDF) polymer via a tape-casting technology. After compositing with PVDF, the thick film retained the ferroelectric polarization behavior, and the PVDF phase had negligible impact on the reflectivity and optical absorption edge of ferroelectric microcrystals. The photoluminescent emission intensities of the characteristic transitions of Sm3+ exhibited significant enhancement after electric polarization, with a maximum modulation ratio exceeding 200 %. The underlying luminescence modulation mechanism is discussed. This work proposed a novel strategy for fabrication of flexible composite thick films with coupling behavior between luminescent and ferroelectric properties.

Piezoelectric Properties of As-Spun Poly(vinylidene Fluoride)/Multi-Walled Carbon Nanotube/Zinc Oxide Nanoparticle (PVDF/MWCNT/ZnO) Nanofibrous Films.

Conductive multi-walled carbon nanotubes (MWCNTs) as well as piezoelectric zinc oxide (ZnO) nanoparticles are frequently used as a single additive and dispersed in polyvinylidene fluoride (PVDF) solutions for the fabrication of piezoelectric composite films. In this study, MWCNT/ZnO binary dispersions are used as spinning liquids to fabricate composite nanofibrous films by electrospinning. Binary additives are conducive to increasing the crystallinity, piezoelectric voltage coefficient, and consequent piezoelectricity of as-spun films owing to the stretch-enhanced polarization of the electrospinning process under an applied electric field. PCZ-1.5 film (10 wt. % PVDF/0.1 wt. % MWCNTs/1.5 wt. % ZnO nanoparticles) contains the maximum β-phase content of 79.0% and the highest crystallinity of 87.9% in nanofibers. A sensor using a PCZ-1.5 film as a functional layer generates an open-circuit voltage of 10 V as it is subjected to impact loads with an amplitude of 6 mm at 10 Hz. The piezoelectric sensor reaches a power density of 0.33 μW/cm2 and a force sensitivity of 582 mV/N. In addition, the sensor is successfully applied to test irregular motions of a bending finger and stepping foot. The result indicates that electrospun PVDF/MWCNT/ZnO nanofibrous films are suitable for wearable devices.

Synthesis of hydrophobic silica without traditional aging process to construct the anti-reflective film with ultralow refractive index for improving power conversion efficiency

The fabrication of anti-reflective films to optimize sunlight utilization encounters various challenges. Herein, we have synthesized modified silica with hydrophobic properties, eliminating the conventional aging process to create an anti-reflective film with an ultralow refractive index of 1.05, marking the lowest value reported to date. This innovative methodology reduces tasks that typically require days or weeks to just a few hours, thereby significantly accelerating production. The power conversion efficiency of the photovoltaic device can increase by 6.2 % when coated with this film. This research not only advances the synthesis of silica but also develops anti-reflective films with record-low refractive indices. This breakthrough represents a substantial contribution, highlighting its significant impact on the photovoltaic field.

Solution-Processable MOF-on-MOF System Constructed via Template-Assisted Growth for Ultratrace H2S Detection.

Conductive metal-organic frameworks (c-MOFs) hold promise for highly sensitive sensing systems due to their conductivity and porosity. However, the fabrication of c-MOF thin films with controllable morphology, thickness, and preferential orientation remains a formidable yet ubiquitous challenge. Herein, we propose an innovative template-assisted strategy for constructing MOF-on-MOF (Ni3(HITP)2/NUS-8 (HITP: 2,3,6,7,10,11-hexamino-tri(p-phenylene))) systems with good electrical conductivity, porosity, and solution processability. Leveraging the 2D nature and solution processability of NUS-8, we achieve the controllable self-assembly of Ni3(HITP)2 on NUS-8 nanosheets, producing solution-processable Ni3(HITP)2/NUS-8 nanosheets with a film conductivity of 1.55 × 10-3 S·cm-1 at room temperature. Notably, the excellent solution processability facilitates the fabrication of large-area thin films and printing of intricate patterns with good uniformity, and the Ni3(HITP)2/NUS-8-based system can monitor finger bending. Gas sensors based on Ni3(HITP)2/NUS-8 exhibit high sensitivity (LOD ~ 6 ppb) and selectivity towards ultratrace H2S at room temperature, attributed to the coupling between Ni3(HITP)2 and NUS-8 and the redox reaction with H2S. This approach not only unlocks the potential of stacking different MOF layers in a sequence to generate functionalities that cannot be achieved by a single MOF, but also provides novel avenues for the scalable integration of MOFs in miniaturized devices with salient sensing performance.

Improved electrochromic device based on mesoporous TiO2 and NiO films

Fabrication of electrochromic films with micro/nanostructures is one of the most feasible ways to improve their properties for high-performance electrochromic devices (ECDs). In this work, mesoporous TiO2 and NiO electrochromic films are prepared by sol-gel technique with an auxiliary solvent of F108 (PEO[Formula: see text]PPO[Formula: see text]PEO[Formula: see text]). By adjusting the content of F108 and heat treatment temperature, the transparent and uniform mesoporous films are successfully prepared. The TiO2 and NiO films are composed of inter-connected nanoparticles with a size of about 20 nm. The thicknesses of the films are about 300 nm and the mesoporous sizes are about 13 nm. The films have a short response time during the electrochromic process. When supplied with positive/negative voltages for 50 s, the coloring/bleaching times of TiO2 and NiO mesoporous films are 15/13 and 17/12 s, respectively. The ECD fabricated with TiO2 and NiO mesoporous films shows good electrochromic properties: short response time (14/19 s, for bleaching/coloring time), wide transmittance modulation range ([Formula: see text]37.21% at 540 nm), high coloration efficiency (CE) (100.6 cm2/C at 540 nm) and outstanding cycle stability (800 cycles). These are attributed to the mesoporous channels of films, which can increase reaction activity site, shorten ions transport path, and thus improve electrochromic reaction.

Mechanically Adaptive Metal-Coordinated Electrogel Membranes.

Achieving specific mechanical properties of hydrogels, especially when used as thin films, can be crucial in diverse applications, including tissue engineering and bioelectronics. Here, a novel electrochemical approach for fabricating uniform and robust hydrogel films based on carboxymethyl cellulose cross-linked by Fe3+ ions (Fe-CMC), exhibiting tunable, dynamic properties is introduced. High modulation of the mechanical properties of the film is achieved by applying multiple electrochemical pulses of oxidative voltage during hydrogel deposition. Our study shows also a remarkable effect of the ionic strength on the properties of the electrodeposited hydrogel films. We found that switching from a salt solution to water enhanced the stiffness of the hydrogels, thereby regulating the permeability of the films. These results are supported by molecular dynamics (MD) simulations, showing that an increase in the ionic strength induces a weakening of the Fe-CMC interactions, ultimately affecting the network strength. Finally, the robustness of these electrodeposited hydrogel films enables their delamination from the electrode without any damage, thereby expanding their potential applications as freestanding smart membranes. By providing fundamental insights into the dynamics of metal-coordinated bonds and their response at the macroscopic scale, we have demonstrated the versatility of electrochemical gelation for the fabrication of robust hydrogel films with tunable mechanical properties, which could serve as smart platforms for a variety of biomedical applications.

Fabrication of l-proline enriched alginate dialdehyde-gelatin hydrogel thin films for efficient wound healing applications.

Hydrogel-based wound management systems represent a promising avenue in tissue engineering for restoring and preserving the normal functionality of damaged tissues. Incorporating active components into hydrogel matrices enhances their suitability for biomedical applications. In this study, we investigated the integration of l-proline, a nonessential imino acid with largely unexplored roles in living systems, into alginate dialdehyde-gelatin hydrogel for wound healing purposes. Physicochemical properties of the resulting hydrogel film, termed ADAGLP, were meticulously evaluated, including wound healing efficacy in vitro and anti-biofilm activity against Gram-positive and Gram-negative microorganisms. Fourier-transform infrared spectroscopy (FTIR) analysis provided insights into the interaction between l-proline and ADAG. Films incorporating 0.5% l-proline were selected for comprehensive investigation. Comparative analysis revealed prolonged gelation time and increased water holding capacity of ADAGLP compared to ADAG films. Moreover, ADAGLP exhibited a significantly higher degradation rate (69.5 ± 3.2%) compared to ADAG (35.2 ± 1.6%). Remarkably, ADAGLP demonstrated cyto-compatibility, non-toxicity, and facilitated migration to the scratch area in vitro conditions. Notably, it exhibited potent anti-biofilm properties. Our findings suggest that ADAGLP hydrogel holds promise as a biomaterial for wound care, offering prolonged drug delivery and maintaining optimal moisture levels in wound areas. The incorporation of l-proline in the wound microenvironment may contribute to enhanced tissue remodeling, by inhibiting biofilm formation, further highlighting the potential of this hydrogel system in wound healing applications.

Solvent-Engineering-Assisted Ligand Exchange Strategy for High-Efficiency AgBiS2 Quantum Dot Solar Cells.

As the initial synthesized colloidal quantum dots (CQDs) are generally capped with insulating ligands, ligand exchange strategies are essential in the fabrication of CQD films for solar cells, which can regulate the surface chemical states of CQDs to make them more suitable for thin-film optoelectronic devices. However, uncontrollable surface adsorption of water molecules during the ligand exchange process introduces new defect sites, thereby impairing the resultant device performance, which attracts more efforts devoted to it but remains a puzzle. Here, we develop a solvent-engineering-assisted ligand exchange strategy to revamp the surface adsorption, improve the exchange efficiency, and modulate the surface chemistry for the environmentally friendly lead-free silver bismuth disulfide (AgBiS2) CQDs. The optimized AgBiS2 CQD solar cells deliver an outstanding champion power conversion efficiency (PCE) of up to 8.95% and improved long-term stability. Our strategy is less environment-dependent and can produce solar cells with negligible performance variance for several batches across several months. Our work demonstrates the critical role of solvents for ligand exchange in the surface chemistry of CQDs and the realization of high-performance photovoltaic devices in a highly reproducible manner.

Orientation optimization for high performance Mg3Sb2 thermoelectric films via thermal evaporation

Low-cost, highly efficient thermoelectric thin-film materials are becoming increasingly popular as miniaturization progresses. Mg3Sb2has great potential due to its low cost and high performance. However, the fabrication of Mg3Sb2thin films with high power factors (PFs) poses a certain challenge. In this work, we propose a general approach to prepare Mg3Sb2thin films with excellent thermoelectric properties. Using a two-step thermal evaporation and rapid annealing process, (001)-oriented Mg3Sb2thin films are fabricated onc-plane-oriented Al2O3substrates. The structure of the film orientation is optimized by controlling the film thickness, which modulates the thermoelectric performance. The PF of the Mg3Sb2at 500 nm (14μW·m-1·K-2) would increase to 169μW·m-1·K-2with Ag doping (Mg3Ag0.02Sb2) at room temperature. This work provides a new strategy for the development of high-performance thermoelectric thin films at room temperature.

Unraveling the Intrinsic Thermal Behavior of Freestanding Ionomer Films Depending on Thickness from Commercial Membrane to Nanofilm.

Proton exchange membrane fuel cells (PEMFCs) for automotive applications are required to achieve mechanical reliability at various temperatures ranging from subfreezing to 80 °C. The thermal behavior of the electrode should be considered at the initial design stage to design a robust automotive fuel cell electrode. Recently, a behavior different from that of the bulk state has been reported for ionomers with a few nanometers of thickness. Therefore, the intrinsic thermal behavior of ionomer films with thicknesses from micrometers to nanometers is quantitatively investigated in this study. By introducing the fabrication of a pseudo-freestanding Nafion thin film and in-plane thermal strain measurement method on the water surface, the thermal expansion of the freestanding Nafion thin film was successfully measured with minimizing substrate constraints. Thermal strain measurement and X-ray scattering studies revealed that the weakening of intermolecular interaction within the hydrophobic and hydrophilic domains in the Nafion thin film caused thermal expansion, and well-structured hydrophobic domains could suppress thermal expansion. The thermal expansion behavior with different heat treatments provides evidence of the thin-film-to-bulk transition of the fully hydrated Nafion film. Intrinsic thermal behavior without substrate interactions can facilitate an understanding of the thermal behavior of electrodes and provide insight into designing a robust PEMFC in temperature-varying environments.

Strategies for alkali-free synthesis, surface modification, and electrophoretic deposition of composite films for biomedical applications

This investigation addresses increasing interest in composites for biomedical applications and advanced methods for their synthesis and electrophoretic deposition (EPD). The feasibility of preparation of hydroxyapatite (HA), titania and zirconia particles using branched polyethylenimine polymer (BPEI) or L-arginine amino acid as organic alkalizers is demonstrated. In this new approach, BPEI and L-arginine are used as alkalizers-capping agents instead of inorganic alkalis. The use of BPEI facilitates synthesis of HA nanorods with reduced size. This approach opens an avenue for the fabrication of nanoparticles of other functional inorganic materials using alkalizers-capping agents. It offers advantages of simple procedure, environmental benefits and improved control of particle size. Composite films are obtained by cathodic EPD using linear polyethylenimine (LPEI) as a charging and film-forming agent. A conceptually new approach is developed for anodic EPD of alginic acid polymer (AlgH) and composite films containing drug molecules in AlgH matrix. This strategy involves the use of L-arginine as an alkalizer for solubilization of drugs, which exhibit poor solubility in water. AlgH and drug molecules are solubilized in water and deposited by anodic EPD. Testing results confirm the fabrication of composite films, containing drug molecules. This method allows reduced gas evolution at the electrode, elimination of film porosity, improved stabilization of bioceramic particles in polymer solutions and facilitates composite film formation from stable suspensions. The deposition methods developed in this investigation can be used for deposition of other cationic and anionic polymers and their co-EPD with bioceramics, drugs and other functional materials.

Enhanced grain orientation in Sb2Se3 thin films deposited on Mo/BSG substrates via RF-sputtering and selenization

The alignment of the Sb2Se3 absorber grains along the c-axis, resulting from their quasi-1D ribbon-like growth, has been found to enhance current density, thereby enabling high power conversion efficiencies in Sb2Se3-based thin film solar cells. This study presents a controllable method for depositing Sb2Se3 thin films with highly oriented grains and a compact morphology, making them suitable for large-scale solar cell applications. A combination of magnetron sputtering and post-deposition isothermal selenization techniques was used. This process involved sputtering antimony onto Mo-coated Borosilicate glass (BSG) substrates, followed by selenizing the films at different temperatures in argon-gas filled quartz ampoules. The influence of several partial Ar-gas pressures and selenization temperatures on the grain growth was studied to achieve enhanced preferred grain orientations and compact morphology of the Sb2Se3 thin films. Selenization at 380 °C resulted in dominant vertical grain orientations with respect to the substrate surface of the Sb2Se3, as confirmed by scanning electron microscopy and X-ray diffraction analysis, without compromising surface compactness. Although occasional micro-voids remain in the films, further optimization could eliminate these imperfections. The developed sequential method, where Sb layer was deposited by RF-sputtering process, followed by an annealing at elevated temperature in the presence of Se and argon gas pressure, holds potential for large-scale production and the fabrication of other quasi-1D chalcogenide thin films.

Utilization of the easy electron-losing capacity of dog fur waste for green energy devices and self-powered smart pet care systems

The present global energy shortage and climate crisis can be addressed by embracing recycling, reuse, and recovery; for example, this can be achieved by methodically utilizing the problematic wastes for energy harvesting. This research describes a novel approach for recovery and reutilization of waste material by incorporating dog fur waste into a triboelectric energy harvester; this was accomplished via a simple, inexpensive, and eco-friendly chemical processing to turn this problematic waste into a high-performance tribolayer. Due to the complications of operating practical devices with dog fur in its natural form, the dog fur waste was transformed for the first time into a uniform thin-film-based high-performance positive tribolayer. The optimization of the fabrication of the dog fur film featured hexagonal pyramid nanostructures, and a novel tribopair was selected and consisted of the dog fur-based film and a Teflon film; these films have very large differences in electron affinities. Based on this optimization and selection, we achieved an outstanding output voltage, current, and power density of 2021.46 V, 109.84 μA and 24,669.957 μWcm−2, respectively, along with appreciable mechanical stability during continuous operation up to 10,000 cycles. Our research demonstrates the potential for integration of green electronics and self-powered human-pet interaction systems while providing a sustainable approach to a circular bioeconomy.

Waste milk-derived biodegradable mulch film fabrication and nutrient slow-release performance evaluation

Petroleum-based polyethylene (PE) plastic was widely used as mulch film and caused severe environmental issue, the purpose of this work was to fabricate a biodegradable mulch film (BMF) using waste milk. Firstly, waste milk was treated by potassium persulfate (PS)/KOH to obtain product rich in nutritional polymers (fulvic/humic-like acids) and K+. The product was used as the main substrate to fabricate multinutrient slow-release biodegradable mulch film (HPBMF) by mixing with gelatin, tributyl citrate, ZnO, and (NH4)2SO4. Therein, polymers in product could crosslink with gelatin to form interpenetrating network structure through hydrogen bonding. The as-prepared HPBMF showed good water resistance as well as mechanical properties including stiffness and flexibility. Owing to observed excellent heat/water retention and nutrition slow-release behavior, HPBMF could effectively increase the yields of chickweeds by 225.9 % and 68 % compared with Blank and PE film (PEF). After use, residual fragments further showed significant fertilization effect. Notably, the HPBMF could be degraded in 3–4 months during application, well matching crop season. Attractively, HPBMF had a lower comprehensive cost than PEF and polylactic acid mulch film. Overall, this work provided a “three birds with one stone” approach to realize plastic pollution mitigation, food waste recycling, and nutrition sustainable supply simultaneously.

Investigating the role of Ag-doped ZnO thin films in UV photodetectors produced via laser assisted chemical bath growth technique

This study introduces the innovative fabrication of Ag-doped ZnO thin films (AgxZnO(100−x) TFs) with varying silver (Ag) concentrations (x) of 0.5, 1.0, 1.5, and 2.0 at% on glass substrates using a simple and cost-effective method known as laser-assisted chemical bath growth (LACBG). This process aims to create metal-semiconductor-metal (MSM) ultraviolet (UV) photodetectors. A continuous wave semiconductor laser with a 444.5 nm wavelength, 5 W power, and 6 min irradiation time was employed to synthesize high-quality Ag-doped ZnO TFs on the glass substrate. Ag electrodes were utilized as Schottky contacts to form MSM UV photodetectors. Structural and morphological analyses conducted using XRD and SEM revealed vertically aligned nanorods and nanoflowers with a high c-axis orientation and hexagonal wurtzite facets, while EDX confirmed Ag incorporation into the ZnO lattice. The UV–Visible absorbance spectra indicated a decrease in bandgap from 3.28 to 2.84 eV with increased Ag content. The current-voltage (I–V) characteristics of the Ag-doped ZnO TFs UV photodetector showed significantly enhanced conductivity at a 2.0 at% concentration level, achieving a responsivity of 10.78 A/W, an external quantum efficiency of 34.67 % at −3 V bias voltage. Finally, the modified device exhibited a sensitivity of 14661.9 %, a gain of 147.62, and a detectivity of 2.25 ×107 Jones, demonstrating its suitability for optoelectronic applications.

Fabrication of edible nanocellulose chitosan bi-component film based on a novel “swell-permeate” approach

The fabrication of multi-component film with colloidal particles could be inconvenient. A novel “swell-permeate” (SP) strategy was proposed to form homogeneous multi-component films. The SP strategy allows colloidal particles to fit into the polymer network by stretching the polymer chains assisted by water. We demonstrated the strategy by creating films with polysaccharide substrates as β-cyclodextrin grafted chitosan (CS) with nanocellulose. The addition of nanocellulose significantly increased the mechanical properties and the barrier performance of the films. The size of nanocellulose particles in affecting mechanical properties was investigated by applying different length of cellulose nanocrystal (CNC), the longer of which, due to denser physical entanglements, showed a better increase to the film in the elastic modulus and tensile strength to 4.54-fold and 5.71-fold, respectively. The films were also loaded with ethyl-p-coumarate (EpCA) and had an enhanced performance in anti-microbial for Altenaria alternata, Salmonella typhi, and Escherichia coli. The anti-oxidative property was increased as well, and both effects were valid both in vitro and in ready-to-eat apples. The strategy provides a practical and convenient method for fabricating colloidal particle containing films, and the novel idea of “swell-permeate” is potentially regarded as a new solution to the challenge of ready-to-eat food quality maintenance.

Fabrication and properties of conductive films based on bacterial cellulose and poly-N-isopropylacrylamide-modified graphene oxide

A conductive film (PNIPAM-rGO/BC) was fabricated combining bacterial cellulose (BC) with poly-N-isopropylacrylamide-modified graphene oxide (PNIPAM-GO) through vacuum filtration and steam reduction techniques. The conductivity and performance of PNIPAM-GO composite and the resulting conductive film were studied. The key findings revealed that PNIPAM-GO composite exhibited a reversible temperature-sensitive behavior. Specifically, the lower critical solution temperature (LCST) increased upon the introduction of graphene oxide (GO). Detailed analyses confirmed uniform dispersion of GO nanosheets within the BC matrix. The incorporation of 10.0 % PNIPAM-GO (containing 7.0 % GO) led to a remarkable 19.6 % increase in tensile strength and approximately 37.0 % enhancement in elongation at break for the conductive film (PNIPAM-rGO/BC) compared to BC. After steam reduction, the electrical conductivity of PNIPAM-rGO/BC exhibited significant improvement over BC. Furthermore, the conductive film demonstrated temperature-dependent conductivity, with a resistivity value approximately 5.2 ± 0.2 KΩ at 25 °C. As the test temperature above the LCST of PNIPAM-GO composite, the resistance decreased. These intriguing temperature-sensitive conductive properties position PNIPAM-rGO/BC as a promising material for smart switches.

Active Stratification of Colloidal Mixtures for Asymmetric Multilayers.

Stratified films offer high performance and multifunctionality, yet achieving fully stratified films remains a challenge. The layer-by-layer method, involving the sequential deposition of each layer, has been commonly utilized for stratified film fabrication. However, this approach is time-consuming, labor-intensive, and prone to leaving defects within the film. Alternatively, the self-stratification process exploiting a drying binary colloidal mixture is intensively developed recently, but it relies on strict operating conditions, typically yielding a heterogeneous interlayer. In this study, an active interfacial stratification process for creating completely stratified nanoparticle (NP) films is introduced. The technique leverages NPs with varying interfacial activity at the air-water interface. With the help of depletion pressure, the lateral compression of NP mixtures at the interface induces individual desorption of less interfacial active NPs into the subphase, while more interfacial active NPs remain at the interface. This simple compression leads to nearly perfect stratified NP films with controllability, universality, and scalability. Combined with a solvent annealing process, the active stratification process enables the fabrication of stratified films comprising a polymeric layer atop a NP layer. This work provides insightful implications for designing drug encapsulation and controlled release, as well as manufacturing transparent and flexible electrodes.

Low-Temperature Fabrication of BiFeO3 Films on Aluminum Foils under a N2-Rich Atmosphere.

To be CMOS-compatible, a low preparation temperature (<500 °C) for ferroelectric films is required. In this study, BiFeO3 films were successfully fabricated at a low annealing temperature (<450 °C) on aluminum foils by a metal-organic decomposition process. The effect of the annealing atmosphere on the performance of BiFeO3 films was assessed at 440 ± 5 °C. By using a N2-rich atmosphere, a large remnant polarization (Pr~78.1 μC/cm2 @ 1165.2 kV/cm), and a high rectangularity (~91.3% @ 1165.2 kV/cm) of the P-E loop, excellent charge-retaining ability of up to 1.0 × 103 s and outstanding fatigue resistance after 1.0 × 109 switching cycles could be observed. By adopting a N2-rich atmosphere and aluminum foil substrates, acceptable electrical properties (Pr~70 μC/cm2 @ 1118.1 kV/cm) of the BiFeO3 films were achieved at the very low annealing temperature of 365 ± 5 °C. These results offer a new approach for lowering the annealing temperature for integrated ferroelectrics in high-density FeRAM applications.