Spin-coated Films Research Articles

Sensing Volatile Pollutants with Spin-Coated Films Made of Pillar[5]arene Derivatives and Data Validation via Artificial Neural Networks.

Different types of solvents, aromatic and aliphatic, are used in many industrial sectors, and long-term exposure to these solvents can lead to many occupational diseases. Therefore, it is of great importance to detect volatile organic compounds (VOCs) using economic and ergonomic techniques. In this study, two macromolecules based on pillar[5]arene, named P[5]-1 and P[5]-2, were synthesized and applied to the detection of six different environmentally volatile pollutants in industry and laboratories. The thin films of the synthesized macrocycles were coated by using the spin coating technique on a suitable substrate under optimum conditions. All compounds and the prepared thin film surfaces were characterized by NMR, Fourier transform infrared (FT-IR), elemental analysis, atomic force microscopy (AFM), scanning electron microscopy (SEM), and contact angle measurements. All vapor sensing measurements were performed via the surface plasmon resonance (SPR) optical technique, and the responses of the P[5]-1 and P[5]-2 thin-film sensors were calculated with ΔI/Io × 100. The responses of the P[5]-1 and P[5]-2 thin-film sensors to dichloromethane vapor were determined to be 7.17 and 4.11, respectively, while the responses to chloroform vapor were calculated to be 5.24 and 2.8, respectively. As a result, these thin-film sensors showed a higher response to dichloromethane and chloroform vapors than to other harmful vapors. The SPR kinetic data for vapors validated that a nonlinear autoregressive neural network was performed with exogenous input for the best molecular modeling by using normalized reflected light intensity values. It can be clearly seen from the correlation coefficient values that the nonlinear autoregressive with exogenous input artificial neural network (NARX-ANN) model for dichloromethane converged more successfully to the experimental data compared to other gases. The correlation coefficient values of the dichloromethane modeling results were approximately 0.99 and 0.98 for P[5]-1 and P[5]-2 thin-film sensors, respectively.

Interplay between Theory and Photophysical Characterization in Symmetric α-Substituted Thienyl BODIPY Molecule.

4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY)-based molecules have emerged as interesting materials for optoelectronic applications due to the possibility to easily fine-tune their photophysical and optical properties, dominated by two main absorption bands in the visible range. However, no studies have been reported on the nature of these spectral features. By means of ultrafast spectroscopy, we detect intramolecular energy transfer in a spin-coated film of di-thieno-phenyl BODIPY (DTPBDP) dispersed in a polystyrene matrix after pumping the high-energy absorption band. The same effect is not present upon pumping the lowest-energy band, which instead allows the achievement of efficient amplified spontaneous emission. Density functional calculations indicate the different nature of the two main absorption bands, explaining their different photophysical behavior.

Metal-organic decomposed lanthanum cerium oxide thin films: A study of chemical and surface properties

Lanthanum cerium oxide thin films have been deposited on n-type (100) silicon wafers using the spin coating technique. The post-deposition annealing was performed over spin-coated films. The compositional studies were conducted by performing Fourier transform infrared spectroscopy, Energy dispersive X-ray spectroscopy, and X-ray diffraction. Ellipsometry was used to determine the thickness and atomic force microscopy was performed to understand the surface morphology of the deposited thin films. The effect of rapid thermal annealing at different temperatures over the structural and chemical properties of the LaCeO2 thin films was observed. The FTIR spectra show the formation of silicates at the interface of the oxide and semiconductor, while XRD results show that the films become crystalline with increased annealing temperature. The refractive index was observed to be reduced with an increase in the annealing temperature and a minor reduction in the physical thickness as per the sample standard deviation of 0.2981[Formula: see text]nm.

Physiochemical and electrical activities of nano copper oxides synthesised via hydrothermal method utilising natural reduction agents for solar cell application

Abstract The aim of this study is to explore the potential compatibility of copper oxide nano-powders synthesised via hydrothermal method for solar cell applications by triggering a reaction between copper acetate and various reducing agents derived from natural resources, including Arabic gum, molasses, starch, and vinegar. X-ray diffraction analysis revealed the crystalline phases of the synthesised materials, indicating the successful synthesis of copper oxide material, which was confirmed by identifying patterns that matched specific copper oxide phases. Fourier transform infrared spectroscopy was employed to analyse the molecular vibrations and chemical compounds present in the reducing agents. The reducing properties of the selected materials and their capacity to convert copper acetate into copper oxide were validated. Field-emission microscopy and transmission electron microscopy analyses of the synthesised copper oxide nanoparticles (NPs) revealed variations in particle size and morphology. These variations were dependent on the particular reducing agent utilised during synthesis. Moreover, the carrier concentration, mobility, and resistivity were evaluated as the electrical properties of the spin-coated copper oxide thin films. Hall effect analysis determined that the choice of reducing agent significantly influenced the carrier concentration (n) and mobility (µ) of the films. Remarkably, nano copper oxide films synthesised using starch exhibited irregular spherical grains with porous surfaces. Starch-synthesised samples showed the highest conductivity of n = 1.2 × 1019 cm−3 when compared with those synthesised with other reducing agents. This suggests that the porous surfaces in the starch-synthesised films may have contributed to their enhanced conductivity compared to films synthesised with alternative reducing agents. In summary, the findings emphasised the influence of the reducing agent on the size, morphology, and electrical conductivity of the copper oxide NPs.

Triboelectric power generation performance of polyvinyl alcohol using ZnO–CuO–AgO trimetallic nanoparticles

AbstractTriboelectric nanogenerators (TENGs), a new technology for gathering sustainable energy, have attracted much scientific interest. In this study, we describe a unique method for modifying the triboelectric power generation performance of Polyvinyl Alcohol (PVA) by adding ZnO–CuO–AgO (ZCA) trimetallic nanoparticles to improve the performance of TENGs and answer the requirement for ecologically benign and biodegradable materials. Hydrothermal synthesis adopted to create ZnO–CuO–AgO trimetallic nanoparticles ensures a distinctive structure with a large surface area, essential for enhancing triboelectric power generation. From the AFM results, it is evident that 1% PVA/ZCA showed the highest output voltage of 0.27V. Despite following the general trend, at higher concentrations of ZCA nanofiller in the PVA matrix, the enhancement of output voltage is not observed, which can be attributed to the non-uniform distribution. The effect of spin-coated film thickness and nanoparticle concentration on the triboelectric performance of the PVA nanogenerator is studied by monitoring the open-circuit voltage in response to various mechanical stimuli. Finally, the developed biodegradable nanogenerators in this study can be used for sustainable energy harvesting applications such as wearable electronics, self-powered sensors, and environmental monitoring systems.

Simultaneous Li-Doping and Formation of SnO2-Based Composites with TiO2: Applications for Perovskite Solar Cells.

Tin oxide (SnO2) has been recognized as one of the beneficial components in the electron transport layer (ETL) of lead-halide perovskite solar cells (PSCs) due to its high electron mobility. The SnO2-based thin film serves for electron extraction and transport in the device, induced by light absorption at the perovskite layer. The focus of this paper is on the heat treatment of a nanoaggregate layer of single-nanometer-scale SnO2 particles in combination with another metal-dopant precursor to develop a new process for ETL in PSCs. The combined precursor solution of Li chloride and titanium(IV) isopropoxide (TTIP) was deposited onto the SnO2 layer. We varied the heat treatment conditions of the spin-coated films comprising double layers, i.e., an Li/TTIP precursor layer and SnO2 nanoparticle layer, to understand the effects of nanoparticle interconnection via sintering and the mixing ratio of the Li-dopant on the photovoltaic performance. X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HR-TEM) measurements of the sintered nanoparticles suggested that an Li-doped solid solution of SnO2 with a small amount of TiO2 nanoparticles formed via heating. Interestingly, the bandgap of the Li-doped ETL samples was estimated to be 3.45 eV, indicating a narrower bandgap as compared to that of pure SnO2. This observation also supported the formation of an SnO2/TiO2 solid solution in the ETL. The utilization of such a nanoparticulate SnO2 film in combination with an Li/TTIP precursor could offer a new approach as an alternative to conventional SnO2 electron transport layers for optimizing the performance of lead-halide perovskite solar cells.

Boost the Circularly Polarized Phosphorescence of Chiral Organometallic Platinum Complexes by Hierarchical Assembly into Fibrillar Networks.

Circularly polarized luminescence (CPL)-active molecular materials have drawn increasing attention due to their promising applications for next-generation display and optoelectronic technologies. Currently, it is challenging to obtain CPL materials with both large luminescence dissymmetry factor (glum) and high quantum yield (Φ). A pair of enantiomeric N N C-type Pt(II) complexes (L/D)-1 modified with chiral Leucine methyl ester are presented herein. Though the solutions of these complexes are CPL-inactive, the spin-coated thin films of (L/D)-1 exhibit giantly-amplified circularly polarized phosphorescences with |glum| of 0.53 at 560 nm and Φair of ~50 %, as well as appealing circular dichroism (CD) signals with the maximum absorption dissymmetry factor |gabs| of 0.37-0.43 at 480 nm. This superior CPL performance benefits from the hierarchical formation of crystalline fibrillar networks upon spin coating. Comparative studies of another pair of chiral Pt(II) complexes (L/D)-2 with a symmetric N C N coordination mode suggest that the asymmetric N N C coordination of (L/D)-1 are favorable for the efficient exciton delocalization to amplify the CPL performance. Optical applications of the thin films of (L/D)-1 in CPL-contrast imaging and inducing CP light generation from achiral emitters and common light-emitting diode lamps have been successfully realized.

Optical characterization of high-quality spin-Coated PVA nanostructured films for photo-sensing application

In our investigation, we fabricated high-quality Polyvinyl Alcohol (PVA) films via spin coating on a variety of substrates, with a focus on their potential applications in diverse devices. Through comprehensive characterization techniques, including spectrophotometer measurements, we evaluated the nanostructure and quality of these films. Our analysis revealed a distinct energy gap of 1.74 eV and a significant 5.37 eV direct allowed optical transition, shedding light on the correlation between absorption coefficient and photon energy. Additionally, we meticulously calculated dispersion parameters using the Wemple-DiDomenico relation, obtaining values of 19.1 eV for dispersion energy and 9.48 eV for oscillator energy under the single oscillator model. These results provide further validation of the unique structural characteristics of PVA films. Importantly, our findings underscore the potential of these materials for advanced optoelectronic devices, particularly in the realm of photosensor applications.

Insights into the Physical Characteristics of Spin Coating Films of Organometallic Materials Based on Phthalocyanine with Nickel, Copper, Manganese and Silicon

Insights into the Physical Characteristics of Spin Coating Films of Organometallic Materials Based on Phthalocyanine with Nickel, Copper, Manganese and Silicon

Amplified Circularly Polarized Luminescence Behavior in Chiral Co-assembled Liquid Crystal Polymer Films via the Strategic Manipulation of Chiral Inducers.

One of the most important factors for the future application of circularly polarized luminescence (CPL) materials is their high dissymmetry factors (gem), and more and more studies are working tirelessly to focus on increasing the gem value. Herein, we chose an achiral liquid crystal polymer (LC-P) and two chiral binaphthyl-based inducers (R/S-3 and R/S-6) with different substitution positions (3,3' positions for R/S-3 and 6,6' positions for R/S-6) to construct chiral co-assemblies and explored their induced amplification CPL behaviors. Interestingly, after the thermal annealing treatment, this kind of chiral co-assembly (R/S-3)0.05-(LC-P)0.95 can emit a superior CPL signal (|gem| = 0.31 and λem = 424 nm), which achieves about 13-fold signal amplification in the spin-coated film, compared to (R/S-6)0.1-(LC-P)0.9 (|gem| = 0.023 and λem = 424 nm). This is because (R/S-3)0.05-(LC-P)0.95 could further co-assemble to form a more ordered arrangement LC state and generate regular helix nanofibers than that of (R/S-6)0.1-(LC-P)0.9. This work provides an efficient method for synthesizing high-quality CPL-active materials through the strategic manipulation of the structure of chiral binaphthyl-based inducers in chiral co-assembled LCP systems.

Tunable circularly polarized luminescence behaviors caused by the structural symmetry of achiral pyrene-based emitters in chiral co-assembled systems

The regulation of circularly polarized luminescence (CPL) behavior is of great significance for practical applications. Herein, we deliberately designed three achiral pyrene derivatives (Py-1, Py-2, and Py-3) with different butoxy-phenyl substituents and the chiral binaphthyl-based inducer (R/S-B) with anchored dihedral angle to construct chiral co-assemblies, and explored their induced CPL behaviors. Interestingly, the resulting co-assemblies demonstrate tunable CPL emission behaviors caused by the structural symmetry effect of achiral pyrene-based emitters during the chiral co-assembly process. And in spin-coated films, the dissymmetry factor (gem) values were 9.1 × 10-3 for (R/S-B)1-(Py-1)10, 5.6 × 10-2 for (R/S-B)1-(Py-2)7, and 8.6 × 10-4 for (R/S-B)1-(Py-3)1, respectively. The strongest CPL emission (|gem| = 5.6 × 10-2, λem = 423 nm, QY = 34.8 %) was detected on (R/S-B)1-(Py-2)7 due to the formation of regular and ordered helical nanofibers through the strong π-π stacking interaction between the R/S-B and the achiral Py-2 emitter. The strategy presented here provides a creative approach for progressively regulating CPL emission behaviors in the chiral co-assembly process.

Unraveling the Molecular Weight Dependence of High Magnetic Field to Manipulate the Semiconducting Polymer Molecular Orientation.

The magnetic alignment of molecules, which exploits the anisotropy of diamagnetic susceptibility, provides a clean and versatile approach to the structural manipulation of semiconducting polymers. Here, the magnetic-alignment dynamics of two molecular-weight (MW) batches of a diketopyrrolopyrrole (DPP)-based copolymer (PDVT-8) were investigated. Microstructural characterizations revealed that the magnetically aligned, high-MW (Mn = 53.7 kDa) PDVT-8 film exhibited a higher degree of backbone chain alignment and film crystallinity compared with the low-MW (Mn = 17.6 kDa) PDVT-8 film grown via the same magnetic alignment method. We found that as the MW increases, the degree of preaggregation of the polymer molecules in solution significantly increases and the aggregation mode changes from H-aggregation to J-aggregation through a cooperative assembly mechanism. These events improved the responsiveness of high-MW polymer molecules to magnetic fields. Field-effect transistors based on the magnetic aligned high-MW PDVT-8 films exhibited a 6.8-fold increase in hole mobility compared to the spin-coated films, along with a mobility anisotropy ratio of 12.6. This work establishes a significant correlation among chain aggregation behavior in solution, polymer film microstructures, magnetic responsiveness, and carrier transport performance in donor-acceptor polymer systems.

Nanostructured tungsten trioxide developed from environmentally friendly green process as a promising cathode for excellent field emission

Extensively explored as cathodes for field emission, nanostructured metal oxides play a crucial role in diverse applications such as microwave amplifiers, renewable energy systems, flat panel displays, and micro-electronics. The quest for high current density, low threshold field, and stable field emission persists. In present study, we introduce a green synthesis approach using vegetable oil as a reaction medium to produce hexagonal tungsten trioxide (h-WO3). The structural analysis confirmed the formation of h-WO3 with a nanorod-like morphology. The spin-coated h-WO3 film on a silicon substrate exhibited promising field emission properties, including a field enhancement factor (β) of 1596 and a turn-on field of 4.60 V/μm, comparable to reported values. This research opens avenues for the cost-effective and scalable utilization of h-WO3 as an electron emitter in advanced optical and electrical devices.

Advancing spin-coating technique for semi-crystalline low-density polyethylene thin films

Polymeric thin films are widely used for coating substrates or as freestanding materials. They are prepared using physical/chemical vapor deposition, dip coating, solution casting, or spin coating. Among these, spin-coated films offer uniform thickness and reproducible results. These films are typically made from amorphous polymers, which are soluble in solvents at ambient temperature, making it easier to coat the polymer solution on the substrate. Despite the advantages of this technique, it has hardly been used for semi-crystalline polymers. In this work, we report the synthesis of freestanding porous thin films using semi-crystalline polymers, specifically low-density polyethylene (LDPE), through the utilization of spin coating. The effect of polymer concentration and porosity on thickness and strength was investigated. The as-prepared thin film was characterized by XRD, XPS, FTIR, and SEM techniques. The increase in crystallinity (14 % change) of the thin film was attributed to the rearrangement and uniform alignment of the polymer chains, which further resulted in relatively higher tensile strength.

Synthesis and biological properties of novel glucose-based fluoro segmented macromolecular architectures

The emergence of novel well-defined biological macromolecular architectures containing fluorine moieties displaying superior functionalities can satisfactorily address many biomedical challenges. In this research, ABA- and AB-type glucose-based biological macromolecules were synthesized using acryl-2,3,4,6-tetra-O-acetyl-D-glucopyranoside with pentafluorophenyl (FPM), pentafluorobenzyl (FBM), phenyl (PM) and benzyl (BM) methacrylate-based macro-RAFT agents following RAFT polymerization. The macro-RAFT agents and the corresponding copolymers were characterized by 19F, 1H, and 13C NMR and FTIR spectroscopic techniques to understand the chemical structure, molecular weight by size-exclusion chromatography, thermal analysis by TGA and DSC. Thermal stability (Td5%) of the FPM and FBM fluoro-based polymers was observed in the range of 219–267 °C, while the non-fluoro PM and BM polymers exhibited in the range of 216–264 °C. Among the macro-RAFT agents, PFPM (107 °C, ΔH: 0.613 J/g) and PPM (103 °C, ΔH: 0.455 J/g) showed higher Tm values, while among the block copolymers, PFBM-b-PG (123 °C, ΔH: 0.412 J/g) and PG-b-PFPM-b-PG (126 °C, ΔH: 0.525 J/g) exhibited higher Tm values. PFBMT and PPM macro-RAFT agents, PPM-b-PG and PG-b-PPM-b-PG copolymer spin-coated films showed the highest hydrophobicity (120°) among the synthesized polymers. The block copolymers exhibited self-assembled segregation by using relatively hydrophobic segments as the core and hydrophilic moieties as the corona. Synthesized biological macromolecules exhibit maximum antibacterial activity towards S. aureus than E. coli bacteria. Fluorophenyl (PFPM) and non-fluorobenzyl-based (PBMT) macro-RAFT agents exhibit low IC50 values, suggesting high cytotoxicity. All the triblock copolymers exhibit lesser cytotoxicity than the di-block polymers.

Determining Structures of Layer-by-Layer Spin-Coated Zinc Dicarboxylate-Based Metal-Organic Thin Films.

Thin films of crystalline solids with substantial free volume built from organic chromophores and metal secondary building units (SBUs) are promising for engineering new optoelectronic properties through control of interchromophore coupling. Zn-based SBUs are especially relevant in this case because they avoid quenching the chromophore's luminescence. We find that layer-by-layer spin-coating using Zn acetate dihydrate and benzene-1,4-dicarboxylic acid (H2BDC) and biphenyl-4,4'-dicarboxylic acid (H2BPDC) linkers readily produces crystalline thin films. However, analysis of the grazing-incidence wide-angle X-ray scattering (GIWAXS) data reveals the structures of these films vary significantly with the linker, and with the metal-to-linker molar ratio used for fabrication. Under equimolar conditions, H2BPDC creates a type of structure like that proposed for SURMOF-2, whereas H2BDC generates a different metal-hydroxide-organic framework. Large excess of Zn2+ ions causes the growth of layered zinc hydroxides, irrespective of the linker used. Density functional theory (DFT) calculations provide structural models with minimum total energy that are consistent with the experimentally observed diffractograms. In the broader sense, this work illustrates the importance in this field of careful structure determination, e. g., by utilizing GIWAXS and DFT simulations to determine the structure of the obtained crystalline metal-organic thin films, such that properties can be rationally engineered and explained.

Control of Lateral Assembly and Vertical Stacking in Spin-Coated Lead Halide Perovskite Nanocrystal Films for Enhanced Photoluminescence Efficiency

Control of Lateral Assembly and Vertical Stacking in Spin-Coated Lead Halide Perovskite Nanocrystal Films for Enhanced Photoluminescence Efficiency

Spin-coated high mobility MoO3 thin film for designing highly efficient lead-free perovskite solar cells

Among the thin film-photovoltaics, perovskite solar cells (PSCs) are one of the most developing topics of research in recent times. Research records reveal that around 26 % efficiency in PSCs has already been achieved so far. However, the commercialization of those PSCs is hindered due to the toxicity of lead (Pb), and the instability of organic cations as well as structural volatility. Several inorganic materials including inorganic hole transport layer (HTL) have recently been proposed and developed to reduce the organic part in the device structure. We fabricate MoO3 thin film materials and conduct a detailed study to realize the potential of MoO3 as a unique HTL for application in PSCs. The synthesis of MoO3 thin film includes several characterization techniques e.g. XRD, FESEM, EDX, UV–Vis, and Hall Effect measurement. We design a MoO3 thin film-based, lead-free PSC structure of FTO/MoO3/PTAA/(FA)2BiCuI6/ZnO/Ag and perform numerical analysis using the SCAPS-1D simulation tool. In the device simulation process, we use the experimentally obtained optoelectrical properties of the MoO3 film and achieve a maximum efficiency of around 22.28 % in a contained lead-free PSC.

Large exchange-driven intrinsic circular dichroism of a chiral 2D hybrid perovskite

In two-dimensional chiral metal-halide perovskites, chiral organic spacers endow structural and optical chirality to the metal-halide sublattice, enabling exquisite control of light, charge, and electron spin. The chiroptical properties of metal-halide perovskites have been measured by transmissive circular dichroism spectroscopy, which necessitates thin-film samples. Here, by developing a reflection-based approach, we characterize the intrinsic, circular polarization-dependent complex refractive index for a prototypical two-dimensional chiral lead-bromide perovskite and report large circular dichroism for single crystals. Comparison with ab initio theory reveals the large circular dichroism arises from the inorganic sublattice rather than the chiral ligand and is an excitonic phenomenon driven by electron-hole exchange interactions, which breaks the degeneracy of transitions between Rashba-Dresselhaus-split bands, resulting in a Cotton effect. Our study suggests that previous data for spin-coated films largely underestimate the optical chirality and provides quantitative insights into the intrinsic optical properties of chiral perovskites for chiroptical and spintronic applications.

Doping a highly charged, water-soluble lanthanide complex into a hydrophobic polymer for the preparation of luminescent films

Doping a highly charged water-soluble complex in a hydrophobic polymethyl methacrylate (PMMA) to form transparent film is demonstrated with using a heptaanionic tri-TbIII complex of thiacalix[4]arene-p-tetrasulfonate (TCAS), formulated as Tb3TCAS2. A bulky hydrophobic countercation, trihexyl(tetradecyl)phosphonium (THTDP+), enabled the isolation of the Tb3TCAS2 salt, which was soluble in a PMMA solution in chloroform. The drop casting of a polymer solution containing 10 wt% THTDP–Tb3TCAS2 salt yielded a transparent film with energy-transfer luminescence. Near-infrared emitting films with Yb3TCAS2 and Nd3TCAS2 were also prepared. The luminescence lifetime (τ) (1.15 ms) of 1.0 wt% Tb3TCAS2-doped PMMA films surpassed that of the salt (0.924 ms), while the luminescence quantum yield (Φ) of the film (0.17) was smaller than that of the salt (0.33). DMSO was the suitable solvent for the salt, providing longer τ (1.40 ms) and larger Φ (0.44) at 0.50 wt%. A low salt concentration in PMMA resulted in a long lifetime. Spin-coated films had longer lifetimes (1.47 ms) at 1.0 wt% owing to a solution-like PMMA environment preventing Tb3TCAS2 aggregation. Drop-casted films had larger Φ values than spin-coated films, as the former might contain salt-like Tb3TCAS2 aggregates.