Liquid-Metal-Based Spin-Coating Exfoliation for Atomically Thin Metal Oxide Synthesis.

Two-dimensional (2D) semiconductors possess exceptional electronic, optical, and magnetic properties, making them highly desirable for widespread applications. However, conventional mechanical exfoliation and epitaxial growth methods are insufficient in meeting the demand for atomically thin films covering large areas while maintaining high quality. Herein, leveraging liquid metal oxidation reaction, we propose a motorized spin-coating exfoliation strategy to efficiently produce large-area 2D metal oxide (2DMO) semiconductors with high crystallinity, atomically thin thickness, and flat surfaces on diverse substrates. Moreover, we realized a 2D gallium oxide-based deep ultraviolet solar-blind photodetector featuring a metal-semiconductor-metal structure, showcasing high responsivity (8.24 A W-1) at 254 nm and excellent sensitivity (4.3 × 1012 cm Hz1/2 W-1). This novel liquid-metal-based spin-coating exfoliation strategy offers great potential for synthesizing atomically thin 2D semiconductors, opening new avenues for future functional electronic and optical applications.

Artificial neural networks in the modeling of the catalytic activity of a biosensor composed of conjugated polymers and urease.

Thin films of conjugated polymer and enzyme can be used to unravel the interaction between components in a biosensor. Using artificial neural networks (ANNs) improves data interpretability and helps construct models with great capacity for classifying and processing information. The present work used kinetic data from the catalytic activity of urease immobilized in different conjugated polymers to create ANN models using time, substrate concentration, and absorbance as input variables since the models had absorbance in a posterior instant as output value to explore the predictivity of the ANNs. The performance of the models was evaluated by Pearson's correlation coefficient (ρ) and mean squared error (MSE) values. After the learning process, a series of new experiments were performed to verify the generality of the models. As the main results, the best ANN model presented 0.9980 and 3.0736 × 10-5 for ρ and MSE, respectively. For the simulation step, intermediary values of substrate concentration were used. The mean absolute percentage error (MAPE) values were 3.34, 3.07, and 3.78 for 12 mM, 22 mM, and 32 mM concentrations, respectively. Overall, with the simulations, it was possible to ascertain the interpolatory capacity of the model, which has a learning mechanism based on absorbance and time as variables. Thus, the potential of ANNs would be in their use in pre-evaluations, helping to determine the substrate concentration at which there is higher catalytic activity or in determining the linear range of the sensor.

Hole Mobility Enhancement in Benzo[1,2-b:4,5-b']Dithiophene-Based Conjugated Polymer Transistors through Directional Alignment, Perovskite Functionalization and Solid-State Electrolyte Gating.

Tunability in electronic and optical properties has been intensively explored for developing conjugated polymers and their applications in organic and perovskite-based electronics. Particularly, the charge carrier mobility of conjugated polymer semiconductors has been deemed to be a vital figure-of-merit for achieving high-performance organic field-effect transistors (OFETs). In this study, the systematic hole carrier mobility improvement of benzo[1,2-b:4,5-b']dithiophene-based conjugated polymer in perovskite-functionalized organic transistors is demonstrated. In conventional OFETs with a poly(methyl methacrylate) (PMMA) gate dielectric, improvements in hole mobility of 0.019 cm2 V-1 s-1 are measured using an off-center spin-coating technique, which exceeds those of on-center counterparts (0.22 ± 0.07 × 10-2 cm2 V-1 s-1). Furthermore, the mobility drastically increases by adopting solid-state electrolyte gating, corresponding to 2.99 ± 1.03 cm2 V-1 s-1 for the control, and the best hole mobility is 8.03 cm2 V-1 s-1 (average ≈ 6.94 ± 0.59 cm2 V-1 s-1) for perovskite-functionalized OFETs with a high current on/off ratio of >106. The achieved device performance would be attributed to the enhanced film crystallinity and charge carrier density in the hybrid perovskite-functionalized organic transistor channel, resulting from the high-capacitance electrolyte dielectric.

New spin coated multilayer lactate biosensor for acidosis monitoring in continuous flow assisted with an electrochemical pH probe.

A LOx-based electrochemical biosensor for high-level lactate determination was developed. For the construction of the biosensor, chitosan and Nafion layers were integrated by using a spin coating procedure, leading to less porous surfaces in comparison with those recorded after a drop casting procedure. The analytical performance of the resulting biosensor for lactate determination was evaluated in batch and flow regime, displaying satisfactory results in both modes ranging from 0.5 to 20 mM concentration range for assessing the lactic acidosis. Finally, the lactate levels in raw serum samples were estimated using the biosensor developed and verified with a blood gas analyzer. Based on these results, the biosensor developed is promising for its use in healthcare environment, after its proper miniaturization. A pH probe based on common polyaniline-based electrochemical sensor was also developed to assist the biosensor for the lactic acidosis monitoring, leading to excellent results in stock solutions ranging from 6.0 to 8.0 mM and raw plasma samples. The results were confirmed by using two different approaches, blood gas analyzer and pH-meter. Consequently, the lactic acidosis monitoring could be achieved in continuous flow regime using both (bio)sensors.

Interaction of Cyanoacrylate with Metal Oxide Surfaces (Cu, Al).

Cyanoacrylates are an extremely reactive class of adhesives. Despite their commercial use as instant adhesives, the adhesion mechanism, especially to technically relevant oxidized metal surfaces, has not yet been sufficiently investigated. In the present work, ultra-thin ethyl cyanoacrylate films are deposited on copper oxide and aluminum oxide by spin coating and cured there. Various surface sensitive spectroscopy methods are used to identify possible interactions. X-Ray photoelectron spectroscopy (XPS) indicates, among other information, hydrogen bonding of the carbonyl group to the oxidized surfaces. Metastable induced electron spectroscopy (MIES) measurements support the theory of this preferential molecular orientation. In addition, XPS shows the presence of an ionic carboxylate (COO- ) species at the interface. Infrared reflection adsorption spectroscopy (IRRAS) measurements confirm this ionic interaction and furthermore allow to investigate the influence of water on the reaction. A possible interaction mechanism of cyanoacrylates with metal oxides could be proposed. The formation of a carboxylate species probably occurs by hydrolysis of the ethyl group via the intermediate of a carboxyl (COOH) species.

Visualizing the Orientation of Single Polymers Induced by Spin-Coating.

The orientation of chains within polymeric materials influences their electrical, mechanical, and thermal properties. While many techniques can infer the orientation distribution of a bulk ensemble, it is challenging to determine this information at the single-chain level, particularly in an environment of otherwise identical polymers. Here, we use single-molecule localization microscopy (SMLM) to visualize the directions of chains within spin-coated polymer films. We find a strong relationship between shear force and the degree and direction of orientation, and additionally, we reveal the effects of chain length and solvent evaporation rate. This work utilizes single-chain resolution to observe the important, though often overlooked, property of chain orientation in the common fabrication process of spin-coating.

Characterization of Molecular Interactions in the Bondline of Composites from Plasma-Treated Aluminum and Wood.

Wood and aluminum composites are becoming increasingly attractive due to their ability to combine the advantages of both materials: the lightweight nature of wood and the strength of aluminum. However, using conventional wood adhesives like polyvinyl acetate (PVAc) to bond these dissimilar materials is challenging and requires special surface treatments. Prior studies have demonstrated that applying a dielectric barrier discharge plasma treatment significantly enhances shear and bending strengths in beech wood/aluminum bonds. This study focuses on the molecular interactions between PVAc and aluminum or beech wood influenced by plasma surface modification. Surface-sensitive methods, including X-ray photoelectron spectroscopy, infrared reflection adsorption spectroscopy and atomic force microscopy, were employed to characterize the PVAc films on the corresponding surfaces and to identify possible interactions. The ultrathin PVAc films required for this purpose were deposited by spin coating on untreated and plasma-treated aluminum. The aluminum surface was cleaned and oxidized by plasma. Additionally, hydroxyl species could be detected on the surface. This can lead to the formation of hydrogen bonds between the aluminum and the carbonyl oxygen of PVAc after plasma treatment, presumably resulting in increased bond strength. Furthermore, the beech wood surface is activated with polar oxygen species.

Ultrafast and Large-Scale Fabrication of PEDOT:PSS Nanofilms Using Electrical-Field-Assisted Direct Ink Deposition.

The importance of conductive polymers has significantly increased over the decade due to their various applications, such as in electronic devices, sensors, and photovoltaics. Poly(3,4-ethylene dioxythiophene) polystyrene sulfonate (PEDOT:PSS) is one of the most successfully and widely used polymers in practical applications. Spin coating is extensively used to fabricate these conductive films; however, it has disadvantages. It is inherently a batch process with relatively low output and high solution wastage. To address these issues, we developed a novel printing process called electrical-field-assisted direct ink deposition (EF-DID), which yields a continuous, homogenous film with high electrical conductivity. In this process, we studied the formation of nanodroplets under an electrical field and their effects on film characteristics. Furthermore, dimethyl sulfoxide (DMSO) was considered as an additive solvent to increase the conductivity and wettability of the films. We then compared EF-DID-printed PEDOT:PSS films with spin-coated films to better understand the film properties. Finally, inverted perovskite solar cell devices were fabricated and compared, where the PEDOT:PSS layers were prepared by EF-DID printing and spin coating. Based on the experimental results, a solution of 20% PEDOT:PSS in DMSO (vol/vol) printed by EF-DID for 15 s provided optimal morphology.

Biominerals Added Bioresorbable Calcium Phosphate Loaded Biopolymer Composites.

Nanocrystalline calcium phosphate (CP) bioceramic coatings and their combination with biopolymers are innovative types of resorbable coatings for load-bearing implants that can promote the integration of metallic implants into human bodies. The nanocrystalline, amorphous CP particles are an advantageous form of the various calcium phosphate phases since they have a faster dissolution rate than that of crystalline hydroxyapatite. Owing to the biomineral additions (Mg, Zn, Sr) in optimized concentrations, the base CP particles became more similar to the mineral phase in human bones (dCP). The effect of biomineral addition into the CaP phases was thoroughly studied. The results showed that the shape, morphology, and amorphous characteristic slightly changed in the case of biomineral addition in low concentrations. The optimized dCP particles were then incorporated into a chosen polycaprolactone (PCL) biopolymer matrix. Very thin, non-continuous, rough layers were formed on the surface of implant substrates via the spin coating method. The SEM elemental mapping proved the perfect incorporation and distribution of dCP particles into the polymer matrix. The bioresorption rate of thin films was followed by corrosion measurements over a long period of time. The corrosion results indicated a faster dissolution rate for the dCP-PCL composite compared to the dCP and CP powder layers.

In Vitro Bioactivity and Antibacterial Effects of a Silver-Containing Mesoporous Bioactive Glass Film on the Surface of Titanium Implants.

Peri-implantitis is defined as a bacterial infection-induced inflammation and suppuration of soft and hard tissues surrounding a dental implant. If bacteria further invade the alveolar bone, they can easily cause bone loss and even lead to the early failure of a dental implant surgery. In the present study, an 80SiO2-15CaO-5P2O5 mesoporous bioactive glass film system containing 1, 5, and 10 mol% of silver was prepared on titanium implant discs (MBG-Ag-coated Ti) using sol-gel and spin coating methods. The wettability and adhesion strength of the films were evaluated using contact angle measurements and adhesion strength tests, respectively. The phase composition, chemical bonding, morphology, and oxidation states of the films were analyzed via X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS), and X-ray photoelectron spectroscopy (XPS). In vitro bioactivity analysis of the films was performed by immersion in a simulated body fluid (SBF) for 24 h. Disk diffusion tests were performed on the early colonizing bacteria Aggregatibacter actinomycetemcomitans and Streptococcus mutans to evaluate the antibacterial ability of the films. A silver-containing mesoporous bioactive glass film with excellent biocompatibility and antibacterial properties was successfully prepared.

Tunable Optical and Multiferroic Properties of Zirconium and Dysprosium Substituted Bismuth Ferrite Thin Films.

This work presents optical and multiferroic properties of bismuth ferrite thin films that are affected by zirconium and dysprosium substitution. Non-centrosymmetric BiFeO3,Bi0.95Zr0.05FeO3, and Bi0.95Dy0.05FeO3 thin films were coated on Pt/TiO2/SiO2/Si substrates using the spin coating method. The crystal structure, optical properties, microstructural, ferromagnetic, and ferroelectric properties of doped bismuth ferrite thin films were systematically investigated. From the XRD patterns, all the prepared thin films matched well with the rhombohedral structure with R3c space group with no observed impurity phases. The average crystallite size of the bismuth ferrite thin films were between 35 and 47 nm, and the size depended on the type of dopant. The determined energy band gap values of BiFeO3, Bi0.95Dy0.05FeO3, and Bi0.95Zr0.05FeO3 thin films were 2.32 eV, 2.3 eV, and 2 eV, respectively. Doping of Dy and Zr at the Bi site led to reduced surface roughness. The prepared thin films exhibited enhanced ferromagnetic and ferroelectric properties. The remnant magnetization of Zr-doped BiFeO3 was greater than that of the BiFeO3 and Dy-doped BiFeO3 thin films. From the obtained results, it was concluded that Zr-doped BiFeO3 thin films are suitable for solar cell fabrication.

Synthesis Methods of Obtaining Materials for Hydrogen Sensors.

The development of hydrogen sensors has acquired a great interest from researchers for safety in fields such as chemical industry, metallurgy, pharmaceutics or power generation, as well as due to hydrogen's introduction as fuel in vehicles. Several types of sensors have been developed for hydrogen detection, including resistive, surface acoustic wave, optical or conductometric sensors. The properties of the material of the sensitive area of the sensor are of great importance for establishing its performance. Besides the nature of the material, an important role for its final properties is played by the synthesis method used and the parameters used during the synthesis. The present paper highlights recent results in the field of hydrogen detection, obtained using four of the well-known synthesis and deposition methods: sol-gel, co-precipitation, spin-coating and pulsed laser deposition (PLD). Sensors with very good results have been achieved by these methods, which gives an encouraging perspective for their use in obtaining commercial hydrogen sensors and their application in common areas for society.

Photoactive Thin-Film Structures of Curcumin, TiO2 and ZnO.

Curcumin is known as a biologically active compound and a possible antimicrobial agent. Here, we combine it with TiO2 and ZnO semiconductors, known for their photocatalytic properties, with an eye towards synergistic photo-harvesting and/or antimicrobial effects. We deposit different nanoscale multi-layer structures of curcumin, TiO2 and ZnO, by combining the solution-based spin-coating (S-C) technique and the gas-phase atomic layer deposition (ALD) and molecular layer deposition (MLD) thin-film techniques. As one of the highlights, we demonstrate for these multi-layer structures a red-shift in the absorbance maximum and an expansion of the absorbance edge as far as the longest visible wavelength region, which activates them for the visible light harvesting. The novel fabrication approaches introduced here should be compatible with, e.g., textile substrates, opening up new horizons for novel applications such as new types of protective masks with thin conformal antimicrobial coatings.

Intrinsic Magnetic Order of Chemically Exfoliated 2D Ruddlesden-Popper Organic-Inorganic Halide Perovskite Ultrathin Films.

Thin film fabrication of 2D layered organic-inorganic hybrid perovskites (2D-OIHPs) for spintronic applications has been attempted using solution-based process like Langmuir-Blodgett technique. However, monolayer or few-layered 2D magnets are not yet realized, even though a wide spectrum of 2D Ruddlesden-Popper (RP) OIHPs are known as quasi-2D Heisenberg magnets in bulk compounds. Here, chemical exfoliation by solvent engineering is applied to successfully synthesize large-sized, few unit-cell-thick 2D RP-OIHPs. Comprehensive structural characterization reveals that binary co-solvents with high relative polarity in spin coating technique are the most effective among nine kinds of solvents. Above all, this enables few-layered 2D RP-OIHP ultrathin films sustaining their intrinsic magnetic order. It is found that XY-like magnetic anisotropy driven by Jahn-Teller effect responsible for ferromagnetism in seven-layered (C6 H5 CH2 CH2 NH3 )2 CuCl4 ultrathin films remains very robust, whereas Ising-like dipolar anisotropy responsible for canted antiferromagnetism in ten-layered (C6 H5 CH2 CH2 NH3 )2 MnCl4 ultrathin films is greatly reduced. It is expected that ferromagnetism even at monolayer limit should be possible by means of further sophisticated solvent engineering as long as Jahn-Teller effect is active. The chemical exfoliation using solvent engineering unambiguously can bring about a new breakthrough in the development of 2D RP-OIHP van der Waals magnets for ultrahigh energy-efficient spintronic, opto-spintronic devices.

Spin-Coated Polysaccharide-Based Multilayered Freestanding Films with Adhesive and Bioactive Moieties.

Freestanding films based on catechol functionalized chitosan (CHI), hyaluronic acid (HA), and bioglass nanoparticles (BGNPs) were developed by spin-coating layer-by-layer assembly (SA-LbL). The catechol groups of 3,4-dihydroxy-l-phenylalanine (DOPA) present in the marine mussels adhesive proteins (MAPs) are the main factors responsible for their characteristic strong wet adhesion. Then, the produced films were cross-linked with genipin to improve their stability in wet state. Overall, the incorporation of BGNPs resulted in thicker and bioactive films, hydrophilic and rougher surfaces, reduced swelling, higher weight loss, and lower stiffness. The incorporation of catechol groups onto the films showed a significant increase in the films' adhesion and stiffness, lower swelling, and weight loss. Interestingly, a synergetic effect on the stiffness increase was observed upon the combined incorporation of BGNPs with catechol-modified polymers, given that such films were the stiffest. Regarding the biological assays, the films exhibited no negative effects on cellular viability, adhesion, and proliferation, and the BGNPs seemed to promote higher cellular metabolic activity. These bioactive LbL freestanding films combine enhanced adhesion with improved mechanical properties and could find applications in the biomedical field, such as guided hard tissue regeneration membranes.

Strategies for Surface Modification with Ag-Shaped Nanoparticles: Electrocatalytic Enhancement of Screen-Printed Electrodes for the Detection of Heavy Metals.

Screen-printed carbon nanofiber electrodes (SPCNFEs) represent an alternative with great acceptance due to their results, as well as their low impact on the environment. In order to improve their performance, in the present work they were modified with silver nanoparticles (Ag-NPs) and electrochemically characterized by using anodic stripping voltammetry. From the Ag-NP synthesis, silver seeds (Ag-NS) and silver nanoprisms (Ag-NPr) were obtained. The Ag-NP formation was confirmed by micrographs, where Ag-NPs with diameters of 12.20 ± 0.04 nm for Ag-NS and 20.40 ± 0.09 nm for Ag-NPr were observed. The electrodes were modified by using three different deposition methods-drop-casting, spin-coating, and in situ approaches-that offer different nanoparticle distribution and electrode modification times. It was observed that the last methodology showed a low amount of Ag-NS deposited on the electrode surface and deep alteration of this surface. Those facts suggest that the in situ synthesis methodology was not appropriate for the determination of heavy metals, and it was discarded. The incorporation of the nanoparticles by spin-coating and drop-casting strategies showed different spatial distribution on the electrode surface, as proved by scanning electron microscopy. The electrodes modified by these strategies were evaluated for the cadmium(II) and lead(II) detection using differential pulse anodic stripping voltammetry, obtaining detection limit values of 2.1 and 2.8 µg·L-1, respectively. The overall results showed that the incorporation route does not directly change the electrocatalytic effect of the nanoparticles, but the shape of these nanoparticles (spherical for seeds and triangular for prisms) has preferential electrocatalytic enhancement over Cd(II) or Pb(II).

Non-Isothermal Sublimation Kinetics of 2,4,6-Trinitrotoluene (TNT) Nanofilms.

Non-isothermal sublimation kinetics of low-volatile materials is more favorable over isothermal data when time is a crucial factor to be considered, especially in the subject of detecting explosives. In this article, we report on the in-situ measurements of the sublimation activation energy for 2,4,6-trinitrotoluene (TNT) continuous nanofilms in air using rising-temperature UV-Vis absorbance spectroscopy at different heating rates. The TNT films were prepared by the spin coating deposition technique. For the first time, the most widely used procedure to determine sublimation rates using thermogravimetry analysis (TGA) and differential scanning calorimetry (DSC) was followed in this work using UV-Vis absorbance spectroscopy. The sublimation kinetics were analyzed using three well-established calculating techniques. The non-isothermal based activation energy values using the Ozawa, Flynn⁻Wall, and Kissinger models were 105.9 ± 1.4 kJ mol-1, 102.1 ± 2.7 kJ mol-1, and 105.8 ± 1.6 kJ mol-1, respectively. The calculated activation energy agreed well with our previously reported isothermally-measured value for TNT nanofilms using UV-Vis absorbance spectroscopy. The results show that the well-established non-isothermal analytical techniques can be successfully applied at a nanoscale to determine sublimation kinetics using absorbance spectroscopy.

Solution-Based Synthesis and Characterization of Cu2ZnSnS4 (CZTS) Thin Films.

Cu2ZnSnS4 (CZTS) ink was synthesized from metal chloride precursors, sulfur, and oleylamine (OLA), as a ligand by a simple and low-cost hot-injection method. Thin films of CZTS were then prepared by spin coating, followed by thermal annealing. The effects of the fabrication parameters, such as ink concentration, spinning rate, and thermal treatment temperatures on the morphology and structural, optical, and electrical properties of the films were investigated. As expected, very thin films, for which the level of transmittance and band-gap values increase, can be obtained either by reducing the concentration of the inks or by increasing the rate of spinning. Moreover, the thermal treatment affects the phase formation and crystallinity of the film, as well as the electrical conductivity, which decreases at a higher temperature.

Advanced Drug-Eluting Poly (Vinyl Chloride) Surfaces Deposited by Spin Coating.

Background and objectives: Medical devices such as catheters are used on a large scale to treat heart and cardiovascular diseases. Unfortunately, they present some important drawbacks (structure failure, calcifications, infections, thrombosis, etc.), with the main side effects occurring due to adhesion and proliferation of bacteria and living cells on the surface of the implanted devices. The aim of this work is to modify the surface of polyvinyl chloride (PVC), an affordable biocompatible material, in order to reduce these aforementioned side effects. Materials and Methods: The surface of PVC was modified by depositing a thin layer also of PVC that incorporates an active substance, dicoumarol (a well-known anticoagulant), by spin coating process. The modified surfaces were analyzed by Fourier-transform infrared (FT-IR) microscopy, Fourier-transform infrared (FT-IR) spectroscopy, Ultraviolet-visible spectroscopy (UV-VIS), and Scanning electron microscopy (SEM) in order to determine the surface morphology and behavior. The samples were tested for Gram-positive (S. aureus ATCC 25923) and Gram-negative (P. aeruginosa ATCC 27853) standard strains from American Type Culture Collection (ATCC). Results: The material obtained had a smooth surface with a uniform distribution of dicoumarol, which is released depending on the deposition parameters. The concentration of dicoumarol at the surface of the material and also the release rate is important for the applications for which the surface modification was designed. PVC modified using the proposed method showed a good ability to prevent salt deposition and decreased the protein adhesion, and the resistance to bacterial adherence was improved compared with standard PVC.

A Purified, Solvent-Intercalated Precursor Complex for Wide-Process-Window Fabrication of Efficient Perovskite Solar Cells and Modules.

A high-purity methylammonium lead iodide complex with intercalated dimethylformamide (DMF) molecules, CH3 NH3 PbI3 ⋅DMF, is introduced as an effective precursor material for fabricating high-quality solution-processed perovskite layers. Spin-coated films of the solvent-intercalated complex dissolved in pure dimethyl sulfoxide (DMSO) yielded thick, dense perovskite layers after thermal annealing. The low volatility of the pure DMSO solvent extended the allowable time for low-speed spin programs and considerably relaxed the precision needed for the antisolvent addition step. An optimized, reliable fabrication method was devised to take advantage of this extended process window and resulted in highly consistent performance of perovskite solar cell devices, with up to 19.8 % power-conversion efficiency (PCE). The optimized method was also used to fabricate a 22.0 cm2 , eight-cell module with 14.2 % PCE (active area) and 8.64 V output (1.08 V/cell).