Optimization of Electrospray Deposition Conditions of ZnO Thin Films for Ammonia Sensing.

This study focuses on the influence of electrospray deposition parameters on the morphology, topography, optical and sensing properties of ZnO films deposited on gold electrodes of quartz crystal resonators. The substrate temperature, precursor feed rate and emitter's voltage were varied. Zinc acetate dehydrate dissolved in a mixture of deionized water, ethanol and acetic acid was used as a precursor. The surface morphology and average roughness of the films were studied by scanning electron microscopy (SEM) and 3D optical profilometry, respectively, while the optical properties were investigated by diffuse reflectance and photoluminescence measurements. The sensing response toward ammonia was tested and verified by the quartz crystal microbalance (QCM) method. The studies demonstrated that electrospray deposition parameters strongly influence the surface morphology, roughness and gas sensing properties of the films. The deposition parameters were optimized in order for the highest sensitivity toward ammonia to be achieved. The successful implementation of the electrospray method as a simple, versatile and low-cost method for deposition of ammonia-sensitive and selective ZnO films used as a sensing medium in QCM sensors was demonstrated and discussed.

Blending Approach Preparation of PVA-g-PMA Films with Embedded "Green" Synthesized Silver Nanoparticles for Acetone Optical Detection.

The blending approach (also known as the ex-situ approach) was used for the deposition of thin composite films comprising poly(vinyl alcohol-graft-methyl acrylate) (PVA-g-PMA) and silver nanoparticles (AgNPs). Firstly, the copolymer aqueous dispersion was synthesized through the redox polymerization of methyl acrylate (MA) on poly(vinyl alcohol) (PVA) using ammonium cerium (IV) nitrate as the initiator. Then, AgNPs were synthesized through a "green" method using the water extract of lavender based on by-products of the essential oil industry, and then they were blended with the polymer. Dynamic light scattering (DLS) and transmission electron microscopy (TEM) were used to determine nanoparticle size, along with their stability over time in suspension, during the 30-day period. Thin films of the PVA-g-PMA copolymer, with different AgNP volume fractions varying between 0.008 and 0.260%, were deposited via the spin-coating method on Si substrates, and their optical properties were explored. UV-VIS-NIR spectroscopy and non-linear curve fitting were used for the determination of the refractive index, extinction coefficient, and thickness of the films, while photoluminescence measurements at room temperature were conducted for studying the emission of the films. The concentration dependence of film thickness was observed and showed that thickness increased linearly from 31 nm to 75 nm when the nanoparticles' weight content increased from 0.3 wt% to 2.3 wt%. The sensing properties toward acetone vapors were tested in a controlled atmosphere by measuring reflectance spectra before and during exposure to the analyte molecules in the same film spot; the swelling degree of films was calculated and compared to the corresponding undoped samples. It was shown that the concentration of AgNPs of 1.2 wt% in the films is optimal for the enhancement of the sensing response toward acetone. The influence of AgNPs on the films' properties was revealed and discussed.

Acetone-Sensitive Thin Films Comprising Coal Fly Ash Na-X Zeolites and Sol-Gel Nb2O5 Matrix.

In this study, thin composite films of a sol-gel Nb2O5 matrix doped with coal fly ash Na-X zeolites were deposited by the spin-coating method. Fly ash of lignite coal collected from the electrostatic precipitators of one of the biggest TPPs in Bulgaria was used as a raw material for obtaining zeolites. Zeolite Na-X was synthesized by ultrasonic-assisted double stage fusion-hydrothermal alkaline conversion of coal fly ash. In order to improve the optical quality and sensing properties of the deposited thin films, synthesized zeolites were wet-milled for 60, 120, and 540 s prior to film deposition. The surface morphology of zeolite powders was studied both by scanning electron microscopy and transmission electron microscopy, while their porosity was investigated by N2-physisorption. Refractive index, extinction coefficient, and thickness of the films were determined through fitting of their reflectance spectra. The sensing ability of thin films towards acetone vapors was tested by measuring the reflectance spectra prior to and during exposure to the analyte, and the change in the reflection coefficient ∆R of the films was calculated. The influence of milling time of zeolites on the sensing and optical properties of the films was assumed and confirmed.

Flexible and Transparent Polymer-Based Optical Humidity Sensor.

Thin spin-coated polymer films of amphiphilic copolymer obtained by partial acetalization of poly (vinyl alcohol) are used as humidity-sensitive media. They are deposited on polymer substrate (PET) in order to obtain a flexible humidity sensor. Pre-metallization of substrate is implemented for increasing the optical contrast of the sensor, thus improving the sensitivity. The morphology of the sensors is studied by surface profiling, while the transparency of the sensor is controlled by transmittance measurements. The sensing behavior is evaluated through monitoring of transmittance values at different levels of relative humidity gradually changing in the range 5-95% and the influence of up to 1000 bending deformations is estimated by determining the hysteresis and sensitivity of the flexible sensor after each set of deformations. The successful development of a flexible sensor for optical monitoring of humidity in a wide humidity range is demonstrated and discussed.

Progress in the Utilization of Coal Fly Ash by Conversion to Zeolites with Green Energy Applications.

Fly ash (FA) from lignite coal combusted in different Thermal Power Plants (TPPs) was used for the synthesis of zeolites (FAZs) of the Na-X type by alkaline activation via three laboratory procedures. FAZs were characterized with respect to their morphology, phase composition and surface properties, which predetermine their suitability for applications as catalysts and adsorbents. FAZs were subsequently modified with metal oxides (CuO) to improve their catalytic properties. The catalytic activity of non-modified and CuO-modified FAZs in the total oxidation of volatile organic compounds was investigated. FAZs were studied for their potential to retain CO2, as their favorable surface characteristics and the presence of iron oxides make them suitable for carbon capture technologies. Thin films of FAZs were deposited by in situ crystallization, and investigated for their morphology and optical sensitivity when exposed to pollutants in the gas phase, e.g., acetone. This study contributes to the development of novel technological solutions for the smart and valuable utilization of FA in the context of the circular economy and green energy production.

Optical Sensing of Humidity Using Polymer Top-Covered Bragg Stacks and Polymer/Metal Thin Film Structures.

Thin films with nanometer thicknesses in the range 100-400 nm are prepared from double hydrophilic copolymers of complex branched structures containing poly(N,N-dimethyl acrylamide) and poly(ethylene oxide) blocks and are used as humidity sensitive media. Instead of using glass or opaque wafer for substrates, polymer thin films are deposited on Bragg stacks and thin (30 nm) sputtered Au-Pd films thus bringing color for the colorless polymer/glass system and enabling transmittance measurements for humidity sensing. All samples are characterized by transmittance measurements at different humidity levels in the range from 5% to 90% relative humidity. Additionally, the humidity induced color change is studied by calculating the color coordinates at different relative humidity using measured spectra of transmittance or reflectance. A special attention is paid to the selection of wavelength(s) of measurements and discriminating between different humidity levels when sensing is performed by measuring transmittance at fixed wavelengths. The influence of initial film thickness, sensor architecture, and measuring configuration on sensitivity is studied. The potential and advantages of using top covered Bragg stacks and polymer/metal thin film structures as humidity sensors with simple optical read-outs are demonstrated and discussed.

Influence of Macromolecular Architecture on the Optical and Humidity-Sensing Properties of Poly(N,N-Dimethylacrylamide)-Based Block Copolymers.

The influence of the macromolecular architecture of block copolymers containing poly(N,N-dimethyl acrylamide) (PDMA) on the optical characteristics and sensing properties of corresponding thin films is discussed. Series of hydrophilic PDMA-based copolymers of different chemical composition and chain architecture such as triblock, star-shaped, and branched were synthesized. The copolymers were characterized using conventional spectroscopic techniques as well as methods for characterization of copolymer macromolecular characteristics in solution, namely size-exclusion chromatography and static light scattering. Thin films of the copolymers of nanometer scale thickness were deposited on silicon substrates by the spin-coating method. The refractive index and extinction coefficient of the copolymer films were calculated from the reflectance spectra by using non-linear curve fitting methods and the composition-structure-optical properties relationships were evaluated. Humidity-sensing properties of the films were studied by measuring reflectance spectra of the films at a relative humidity range from 5 to 95%RH. The implementation of the copolymer films as optical sensors of humidity is justified and discussed.

Vapor responsive one-dimensional photonic crystals from zeolite nanoparticles and metal oxide films for optical sensing.

The preparation of responsive multilayered structures with quarter-wave design based on layer-by-layer deposition of sol-gel derived Nb(2)O(5) films and spin-coated MEL type zeolite is demonstrated. The refractive indices (n) and thicknesses (d) of the layers are determined using non-linear curve fitting of the measured reflectance spectra. Besides, the surface and cross-sectional features of the multilayered structures are characterized by scanning electron microscopy (SEM). The quasi-omnidirectional photonic band for the multilayered structures is predicted theoretically, and confirmed experimentally by reflectance measurements at oblique incidence with polarized light. The sensing properties of the multilayered structures toward acetone are studied by measuring transmittance spectra prior and after vapor exposure. Furthermore, the potential of the one-dimensional photonic crystals based on the multilayered structure consisting of Nb(2)O(5) and MEL type zeolite as a chemical sensor with optical read-out is discussed.

Zeolite films as building blocks for antireflective coatings and vapor responsive Bragg stacks.

Zeolite films (LTL, BEA and MFI) are prepared with a thickness in the range 50-170 nm through a multistep spin-on deposition method. The optical properties of the zeolite films including refractive index, extinction coefficient and thickness are determined from the reflectance spectra using a nonlinear curve fitting method. The total free pore volume of the films using the Bruggeman effective medium theory is calculated. The potential of the zeolite films for broadband antireflection (AR) application is demonstrated. Five times reduction of the reflectance of a silicon substrate covered with the double AR films comprising of MFI type zeolite (120 nm) deposited on Nb2O5 (60 nm) is achieved. Additionally, the MFI zeolite film is used as a building block of vapor responsive Bragg stacks with a strong response towards acetone. The reversible response of the Bragg stacks towards acetone without additional annealing opens up the possibility of preparing sensors with optical read-out by incorporation of sensitive and transducer elements into a single device.