Influence of the preparation process on the electrical properties of high-field co-doped zinc oxide varistors

High-field ZnO/Bi₂O₃ varistors co-doped with Mn and Co were synthesized using a two-step co-precipitating process. A Zn²⁺ solution containing the Mn and Co doping elements was first precipitated into hydroxides, further converted into oxalates and finally calcined to create the doped ZnO phase. Bi³⁺ precipitated at the grain boundaries thanks to an HNO₃ treatment of the ZnO grains. The influence of the precursor type (nitrates or chlorides) and the calcination temperature on the properties of the powders and ceramics were investigated. ICP-AES, microstructural analysis and non-linear voltage measurements were used to characterize the samples. The type of precursor solution was found to have a strong influence on the electrical properties. Furthermore, the calcination temperature modified the microstructure of the powder and consequently also that of the varistor.     

Structure and electrical properties of polymer composites based on tungsten oxide varistor ceramics

Composites based on nonlinear tungsten oxide ceramics and a polyethylene matrix with a volume fraction of ceramic filler from 10 vol % to 43 vol % were studied. It was shown that composites are an isotropic mixture of WO₃ grains in a polymer matrix. The current-voltage characteristics of the composites were nonlinear. Composites have a high positive temperature coefficient of resistance up to 15.8 K^-1 in the temperature range of 40–75 °C. It is shown that the temperature coefficient of resistance is positive and increases with increasing electric field strength. The decrease in the electrical conductivity of composites with increasing temperature is explained by the expansion of the polymer matrix and the rupture of the current-conducting channels between the conducting grains of the varistor ceramics. The dependence of the electrical conductivity of the composite on the volume fraction of varistor ceramics is well described within the framework of a three-dimensional percolation model for a two-phase system.     

Effect of wet screening on particle size distribution and coal properties

Wet screening is one of the methods used to remove fine material from the coal feed to gasification. Sasol Synfuels in South Africa undertook an investigation to quantify fine coal generation in the coal supply to gasification. Coal samples were wet screened in the laboratory and results compared to the normal dry screening procedure. It was found that the fines (−0.5 mm) increased almost five times when the coal was wet screened compared to dry screening. This study was subsequently initiated by Sasol Technology R&D to establish the mechanism of fine coal generation during wet screening, as well as the effect of wet screening on particle size distribution (PSD) and chemical properties of coal. Changes in the PSD and chemical properties of coal from individual coal sources used at Sasol Synfuels were compared. Composite coal samples with a predetermined PSD of all individual coal sources used at Sasol Synfuels were screened under wet and dry conditions. The PSD was again determined after screening, as well as the mineral composition (by X-ray diffraction) of the fines. Results indicated that wet screening caused clay minerals to be removed from the coal structure leading to an increase in the fines. This removal of minerals weakened the coal structure causing further size degradation of coarser fractions.     

Electrical and chemical stability engineering of solution-processed indium zinc oxide thin film transistors via a synergistic approach of annealing duration and self-combustion process

The electrical and chemical stability of solution-processed indium zinc oxide (IZO) channel thin-film transistors (TFTs) were engineered via a synergistic approach of annealing duration and self-combustion process. In particular, the amorphous IZO TFTs that were thermally treated at 400 °C for 3 h using the specific precursor combination to generate internal self-combustion energy showed the best electrical performance [high saturation mobility (μ_SAT)=2.7 cm²/V s] and stability [low threshold voltage shift (ΔV_TH) under positive bias stress of 10.5 V] owing to the formation of oxide films with excellent metal–oxide–metal (M–O–M) bonds, fewer impurities, and an amorphous phase compared to IZO TFTs using other precursor formulas and annealing times. Longer annealing times led to a saturated M–O bond ratio and crystallization via extreme thermal annealing, which induced electrical degradation (low μ_SAT and high ΔV_TH) of IZO TFTs. In the wet chemical patterning of electrodes, conventional acidic and basic wet etchants cause severe damage to the surfaces of the IZO channels; thus, insufficiently annealed IZO TFTs exhibited considerable degradation in terms of their on-current level and mobility. Alternatively, the TFTs subjected to an excessively long-term thermal annealing showed only a moderate decrease in mobility with the formation of small nanocrystals.     

A novel template-free wet chemical synthesis method for economical production of zinc oxide microrods under atmospheric pressure

This work reports a template-free wet chemical synthesis method for economical production of zinc oxide (ZnO) microrods by using an inexpensive polypropylene beaker as a reactor under atmospheric pressure. The morphology and crystal structure of the as-prepared ZnO microrods were investigated by scanning electron microscopy (SEM), X-ray powder diffraction (XRD) and Raman scattering. Fourier-transform infrared (FTIR) spectroscopy, thermogravimetric analysis (TGA), Ultraviolet–visible (UV/Vis) spectroscopy and methylene blue photocatalytic degradation test were also conducted to study their physical and chemical properties. The results show that the as-prepared ZnO microrods have a hexagonal crystal structure. Under the optimal synthesis condition, they have a diameter of 0.8–2.6 μm and a length of 10–40 μm. Compared with commercial ZnO powders, the as-prepared ZnO microrods have a higher whiteness. Meanwhile, the as-prepared ZnO microrods have very low photocatalytic activity, indicating that they have good photostability and are unlikely to cause the photodegradation of polymers such as binders. As a result, they will be an excellent and economical white pigment with great potential in coating applications.     

Effect of Pr on the electrical and chemical properties of cerium oxide prepared by combustion method

Nanoparticles of Ce_1−xPr_xO₂ (X: 0.6 and 0.8), were synthesized by the combustion method using citric acid as chelating and fuel agent. The X-ray diffraction patterns and Rietveld refinements confirm that samples shown as a single phase in a cubic fluorite structure, with an increase in the lattice parameter as a function of Pr concentration. The crystallite size domains obtained by the Scherrer formula, confirm values around 10 and 37 nm. The scanning electron microscopy images, show that the solids are composed of dense heterogeneous aggregates. The X-ray photoelectron spectroscopy, reveals that oxides are composed of cerium and praseodymium cations in oxidation states 4+ and 3+ respectively. The TPR-H₂ profiles indicate that cerium and praseodymium cations present in the obtained systems are completely reduced to Ce³⁺ and Pr³⁺ at temperatures above 790°C. The impedance spectroscopy data at room temperature showed that the conduction processes for the two systems take place at the grain boundaries. The Ce_0.2Pr_0.8O₂ system offer lower resistance, due to the high amount of Pr³⁺ ions inserted in the structure and the high amount of oxygen vacancies formed in the synthesis process.     

Silicon surface wet cleaning and chemical oxide growth by a novel treatment in aqueous chlorine solutions

A few new reactants for the wet cleaning of silicon surfaces, for example, ozone dissolved in ultrapure water (UPW), have been proposed to replace the original RCA process using H₂O₂ solutions. In the present work we describe, for the first time, the mechanism of silicon surface oxidation by dilute solutions of elemental chlorine. Upon reaction with this highly oxidizing agent, the open circuit potential (OCP) shifted immediately to positive values, the effect being identical for both n- and p-type Si substrates. The surface transformation was firstly investigated by electrochemical impedance spectroscopy which showed successive semicircles representing RC equivalent circuits, showing a gradual growth of an insulating layer. X-ray photoelectron spectroscopy (XPS) recordings demonstrated unequivocally the formation of a pure and uniform chemical oxide layer, the possible contamination by Cl element being negligible.Moreover, the strong oxidizing and complexing properties of chlorinated aqueous solutions afford this reactant a high efficiency in surface cleaning from metal impurities. The effectiveness of this treatment was proven by AFM observation of the surface which was beforehand intentionally contaminated by Cu nuclei. The original flat surface was easily restored after a short cleaning using this new chemical reactant.This novel technique of surface treatment is promising with respect to the economy and environmental requirements, and also for the possible subsequent growth of multi-layer high-k dielectric structures.     

Preparation and gas separation properties of asymmetric polysulfone membranes by a dual bath method

Defect-free skinned asymmetric gas separation membranes were prepared by a dual bath coagulation method that is a wet/wet phase inversion technique. The membranes were cast from a polysulfone/N,N-dimethylacetamide solution. In two sequent nonsolvent baths, the first bath using iso-propanol (IPA) leads to the formation of a dense skin top layer and the second bath using water makes the actual polymer precipitation. The top skin layer thickness was governed by changing the immersion time of the first IPA bath. We suggest that the growth rate of the skin layer is to be determined by a diffusion process.     

Predicting and interpreting oxide glass properties by machine learning using large datasets

With the advent of powerful computer simulation techniques, it is time to move from the widely used knowledge-guided empirical methods to approaches driven by data science, mainly machine learning algorithms. We investigated the predictive performance of three machine learning algorithms for six different glass properties. For such, we used an extensive dataset of about 150,000 oxide glasses, which was segmented into smaller datasets for each property investigated. Using the decision tree induction, k-nearest neighbors, and random forest algorithms, selected from a previous study of six algorithms, we induced predictive models for glass transition temperature, liquidus temperature, elastic modulus, thermal expansion coefficient, refractive index, and Abbe number. Moreover, each model was induced with default and tuned hyperparameter values. We demonstrate that, apart from the elastic modulus (which had the smallest training dataset), the induced predictive models for the other five properties yield a comparable uncertainty to the usual data spread. However, for glasses with extremely low or high values of these properties, the prediction uncertainty is significantly higher. Finally, as expected, glasses containing chemical elements that are poorly represented in the training set yielded higher prediction errors. The method developed here calls attention to the success and possible pitfalls of machine learning algorithms. The analysis of the SHAP values indicated the key elements that increase or decrease the value of the modeled properties. It also estimated the maximum possible increase or decrease. Insights gained by this analysis can help empirical compositional tuning and computer-aided inverse design of glass formulations.     

Photoluminescence of zinc oxide nanopowder synthesized by a combustion method

Zinc oxide (ZnO) nanopowder was synthesized by a simple and quick combustion method using zinc nitrate as a precursor and glycine as a fuel material. The starting materials were mixed at room temperature and spontaneous ignition of which resulted into the ZnO nanopowder. The synthesized nanopowder was characterized by X-ray diffraction (XRD), scanning electronic microscope (SEM), Infrared (IR) spectrophotometer and spectroflurometer in order to study the structural, morphological, compositional and photoluminescence (PL) properties. The ZnO powder shows polycrystalline nature with preferential peak (101) having crystallite size 25 nm. A significant band at 532 cm⁻¹ in the IR spectrum corroborates the presence of characteristic band of ZnO. Room temperature photoluminescence spectrum of the synthesized nanopowder exhibits a dominant, sharp and strong ultraviolet (UV) emission with a suppressed deep-level emission indicating good crystal quality and optical properties.     

The effects of Ni-addition on the crystal structure,thermal properties and morphology of Mg-based hydroxyapatites synthesized by a wet chemical method

Four Mg-based hydroxyapatites (HAps) doped with Ni at various amounts of 0, 0.6, 1.2 and 1.8?at% were prepared at the temperature of 870?°C by a wet chemical synthesis. The crystallite size, lattice parameters and crystallinity percent dramatically decreased with adding of Ni. The amount of HAp phase for all the Ni-containing samples is smaller than that of the Ni-free MgHAp. Furthermore, the lattice strain, stress and anisotropic energy density values were affected by the amount of Ni. The differential thermal analysis (DTA) measurements taken in the temperature range from 25 to 1000?°C showed that all the samples are thermally stable. No significant change in the morphology was observed. It was observed that the gradual introduction of Ni caused the Ca-deficiency.     

The sintering behavior,microstructure, and electrical properties of gallium-doped zinc oxide ceramic targets

The properties of sputtering targets have recently been found to affect the performances of sputtered films and the sputtering process. To develop high-quality GZO ceramic targets, the influences of Ga₂O₃ content and sintering temperature on the sintering behavior, microstructure, and electrical properties of GZO ceramic targets were studied.The results showed that the increase in Ga₂O₃ content from 3 wt% (GZO-3Ga) and 5 wt% (GZO-5Ga) not only inhibited the densification but retarded grain growth. During sintering, ZnGa₂O₄ phase formed before 800 °C, and Zn₉Ga₂O₁₂ phase was found after sintering at 1000 °C. Moreover, after sintering at 1200 °C, the number of Zn₉Ga₂O₁₂ precipitates increased at the expense of ZnGa₂O₄ and ZnGa₂O₄ disappearing completely. The relative density, grain size, and resistivity of GZO-3Ga sintered at 1400 °C in air were 99.3%, 3.3 μm, and 2.8 × 10⁻³ Ω cm, respectively. These properties of GZO ceramics are comparable to properties reported in the literature for AZO sintered in air.     

Effect of oxygen chemisorption on the electrical conductivity of zinc oxide films prepared by a spray pyrolysis method

Zinc oxide films (2–3 μm thick) have been deposited on alumina substrates currently used for electronic applications by a spray pyrolysis method. Their electrical resistivity-temperature characteristics were measured in nitrogen, air and oxygen. The data are explained by surface reactions involving zinc and adsorbed oxygen atoms in different forms. The comparison with the electrical response of a similar material in the bulk form is also examined.     

Characterization of Ti/Si binary oxides prepared by the sol-gel method and their photocatalytic properties: The hydrogenation and hydrogenolysis of CH3CCH with H2O

Titanium-silicon (Ti/Si) binary oxides having different Ti content were prepared by the sol-gel method and utilized as photocatalysts for the hydrogenation and hydrogenolysis of CH₂CCH with H₂O. The photocatalytic reactivity and selectivity of these catalysts were investigated as a function of the Ti content and it was found that the hydrogenolysis reaction (C₂H₆ formation) was predominant in regions of low Ti content, while the hydrogenation reaction (C₃H₆ formation) proceeded in regions of high Ti content. The in situ photoluminescence, diffuse reflectance absorption, FT-IR, XAFS (XANES and EXAFS), and XPS spectroscopic investigations of these Ti/Si binary oxides indicated that the titanium oxide species are highly dispersed in the SiO₂ matrices and exist in a tetrahedral coordination exhibiting a characteristic photoluminescence spectrum. The charge transfer excited state of the tetrahedrally coordinated titanium oxide species plays a significant role in the efficient photoreaction with a high selectivity for the hydrogenolysis of CH₃CCH to produces mainly C₂H₆ and CH₄, while the catalysts involving the aggregated octahedrally coordinated titanium oxide species show a high selectivity for the hydrogenation of CH₃CCH to produce C₃H₆, being similar to reactions of the powdered TiO₂ catalysts. The good parallel relationship between the yield of the photoluminescence and the specific photocatalytic reactivity of the Ti/Si binary oxides as a function of the Ti content clearly indicates that the high photocatalytic reactivity of the Ti/Si binary oxides having low Ti content is associated with the high reactivity of the charge transfer excited state of the isolated titanium oxide species in tetrahedral coordination, [Ti³⁺-O⁻]*.     

Growth temperature dependent properties of ZnO nanorod arrays on glass substrate prepared by wet chemical method

In this work, ZnO nanorod arrays were grown on glass substrate by the wet chemical method, and the effect of synthesis temperature on the properties was investigated. The grown nanorods were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FE-SEM), Raman and Photoluminescence (PL) measurements. XRD pattern showed that nanorod prepared at 80 °C and 90 °C has high crystallinity with wurtzite structure and orientated along the c-axis. However, nanorods were not formed at 60 °C and 70 °C due to less energy supply for the growth of the ZnO. FE-SEM results showed that the morphology and the size of ZnO can be effectively controlled. In particular, as the temperature increased, diameter of the nanorod was increased while length decreased. Raman scattering spectra of ZnO nanorod arrays revealed the characteristic E₂^high mode that is related to the vibration of oxygen atoms in the wurtzite ZnO. Room-temperature PL spectra of the ZnO nanorods revealed a near-band-edge (NBE) emission peak. The NBE (UV light emission) band at ~383 nm might be attributed to the recombination of free exciton. The narrow full-width at half-maximum (FWHM) of the UV emission indicated that ZnO nanorods had high crystallinity.     

Effect of rapid thermal annealing on the properties of zinc tin oxide films prepared by plasma-enhanced atomic layer deposition

The effect of rapid thermal annealing treatments on the microstructure, surface morphology, and optical characteristics of zinc tin oxide (ZTO) films produced by plasma-enhanced atomic layer deposition was investigated. The ZTO films were annealed in oxygen atmosphere for 2 min at four selected temperatures from 500 to 800 °C. The X-ray diffraction showed that the annealing temperature has a great influence on the crystalline characteristics of ZTO films. The film shows complete amorphous structure for as-deposited ZTO film. Meanwhile, the spinel zinc stannate Zn₂SnO₄ was obtained for the samples annealed from 500 to 800 °C, which shows polycrystalline nature. The X-ray photoelectron spectroscopy proved that the annealing process in oxygen gas can effectively can reduce the oxygen vacancy defects in the films. In addition, the photoluminescence spectroscopy manifests an ultraviolet emission with a broad peak range from 345 to 385 nm. Moreover, the ultraviolet luminescence intensity increases continuously with the increase of annealing temperature. Spectroscopic ellipsometry analyses demonstrate that the refractive index of annealed films increases as the increase of annealing temperature, while the extinction coefficient decreases gradually with the increase of annealing temperature in the visible light range.     

One dimensional (1-D) signatures of nanopillars and nanowires in niobium doped zinc oxide (NZO) thin films prepared by aerosol assisted chemical vapour deposition (AACVD)

We report for the first time a facile synthesis of niobium (Nb) doped (1-D) ZnO nanopillars and nanowires by aerosol assisted chemical vapour deposition with improved structural and optical properties. The micro structural, vibrational and optical properties of Nb-doped ZnO were investigated by X-ray diffraction (XRD), Raman spectroscopy, Scanning electron microscopy (SEM)/Energy dispersive spectroscopy (EDS) and UV–Vis spectroscopy (UV/VIS). The results presented show that Nb doping and solvent choice can effectively control the growth of ZnO nanostructures as well as their reproducibility. The XRD results revealed that the highest estimated crystallite size of Nb doped ZnO was found to be 4.7 nm from depositions conducted in methanol and 5.4 nm from depositions conducted in toluene for 0.2 M% Nb doping. It is further explored that with an increase of Nb content, ZnO films show poor crystallinity with preferential orientation along the 0 0 2 plane. The change in morphology and local structure of ZnO also led to variations in the vibrational properties of the materials. Upon Nb doping, the A1 (LO) mode of ZnO was found to red shift and broaden, whereas a blue shift was found for the 2A1 (LO), 2E1 (LO) and 2LO vibrational modes. The UV–Visible spectroscopy of Nb doped ZnO revealed that excellent visible transmittance (∼89%) was achievable and witnessed an increase in band gap from 3.3 eV to 3.5 eV with increased Nb doping.     

Effects of Sn4+ doping and oxygen vacancy on magnetic and electrical properties of yttrium iron garnet prepared by sol-gel method

Sn-substituted yttrium iron garnet samples, Y₃Fe_5-xSn_xO₁₂ (x = 0–0.1, step 0.02) were prepared using a citrate sol–gel method and followed by a sintering process. Synchrotron X-ray diffraction (SXRD), X-ray absorption near edge structure (XANES), scanning electron microscope (SEM) and Fourier infrared spectroscopy (FTIR) measurements were used to investigate the structure parameters, valence state of Fe, oxygen vacancies and lattice distortion in the samples. The magnetic properties of the samples were measured with the SQUID and VSM equipments. The Sn substitution and oxygen vacancies cause the transformation of Fe³⁺ to Fe²⁺ which leads to the decrease of Curie temperature and slight increase of saturation magnetization. Temperature dependence of the resistivity in the range of 300–573 K was investigated to elucidate the conduction mechanism in the samples. The resistivity of the sol-gel derived samples was found to be nine orders of magnitudes lower than the value for the bulk sample prepared by flux-grown method. The effects of Fe²⁺ centers, lattice dislocation, porosity and grain boundary on the resistivity are discussed. This study indicates that Sn-substituted yttrium iron garnets are good candidates for sensor elements which operate based on electrical signals.     

Influence of post-annealing atmosphere on microstructure,optical and electrical properties of zinc cadmium oxide films deposited by DC and RF magnetron co-sputtering

Zinc cadmium oxide (Zn_1−xCd_xO) films were deposited on quartz substrates by direct current (DC) and radio frequency (RF) reactive magnetron co-sputtering and the influence of post-annealing atmosphere on their microstructure, optical and electrical properties were investigated by X-ray diffraction (XRD), optical absorbance, photoluminescence (PL) and Hall measurements. Results indicate that the band gap (E_g) of all Zn_1−xCd_xO films annealed in different atmospheres are smaller than that of the undoped ZnO, the observed shifts in E_g being 0.43, 0.37 and 0.32 eV for the Zn_1−xCd_xO films annealed in argon, oxygen and vacuum, respectively. Hall measurement results indicate that all Zn_1−xCd_xO films annealed in different atmospheres show the n-type conduction, but the Zn_1−xCd_xO film annealed in vacuum has low resistivity and high concentration, which has room-temperature resistivity of 1.59 Ω cm and carrier concentration of 2.07×10¹⁷ cm⁻³. Compared with Zn_1−xCd_xO films annealed in oxygen and argon, Zn_1−xCd_xO film annealed in vacuum has the best crystal quality, luminescence and electrical properties. The influencing mechanism of the post-annealing atmosphere on the electrical and optical properties of the Zn_1−xCd_xO film is discussed.