Microstructural, crystal structure and electrical characteristics of shock-consolidated Ga2O3 doped ZnO bulk

Ga₂O₃ (5 wt.%) doped zinc oxide (ZnO, 95 wt.%) bulk was fabricated by underwater shock compaction technique. The microstructural, crystal structure and electrical properties of shock-consolidated samples were investigated and compared to a commercially available sintered Ga₂O₃ (5 wt.%) doped ZnO (95 wt.%). The relative density of shock-consolidated sample was about 97% of the theoretical density, and no grain growth and lattice defects were confirmed. The grain boundary resistance was remarkably higher than that of commercial sintered Ga₂O₃ doped ZnO and nonlinear current-voltage (I-V) characteristics of shock-consolidated ZnO and Ga₂O₃ doped ZnO were very lower than that of commercial ZnO varistor.     

Sintering behaviour of a ZnO waste powder obtained as by-product from brass smelting

The effect of two sintering methods (conventional sintering and two-step sintering) and of alumina addition on the sintering behaviour of a ZnO-rich waste powder (ZnO > 95 wt%), a by-product from brass smelting industry, was studied aiming to improve the sintered density and grain size. Both conventional sintering and two-step sintering methods did not lead to fully dense powder compacts, as densification was conditioned by abnormal grain growth and the particle size of the ZnO-rich residue. When two-step sintering was used the grain growth was reduced comparatively to conventional sintering method. The highest relative sintered density (about 90%) was achieved when samples of ZnO waste and samples of ZnO waste with 2 wt% added Al₂O₃ were processed by two-step sintering and corresponded to a mean grain size of around 18 µm and 7 µm, respectively. XRD and SEM results indicated that alumina addition helped to inhibit grain growth due to the formation of gahnite spinel (ZnAl₂O₄) precipitates in the grain boundaries of zincite (ZnO) grains.     

Hot pressing of nanocrystalline zinc oxide compacts: Densification and grain growth during sintering

Sintering behavior of nanocrystalline zinc oxide (ZnO) powder compacts using hot pressing method was investigated. The sintering conditions (temperature and total time) and results (density and grain size) of two-step sintering (TSS), conventional sintering (CS) and hot pressing (HP) methods were compared. The HP technique versus CS was shown to be a superior method to obtain higher final density (99%), lower sintering temperature, shorter total sintering time and rather fine grain size. The maximum density achieved via HP, TSS and CS methods were 99%, 98.3% and 97%, respectively. The final grain size of samples obtained by HP was greater than that of TSS method. However, the ultra-prolonged sintering total time and the lower final density (88 ks and 98.3%) are the drawbacks of TSS in comparison with the faster HP (17 ks and 99%) method.     

Microstructural and compositional aspects of ZnO-based varistor ceramics prepared by direct mixing of the constituent phases and high-energy milling

ZnO-based varistor samples were prepared by the direct mixing of the constituent phases (DMCP) and sintering at 1100 °C for 2 h. The influence of the starting powder mixture's composition – the amounts of the pre-reacted varistor compounds and their composition – and its preparation, either with or without mechano-chemical activation (MCA), on the microstructure, phase composition and electrical characteristics of the varistor samples was studied. It showed that MCA improved the density and microstructural homogeneity of the varistor samples. MCA strongly affected the grain growth: it enhanced the nucleation of inversion boundaries (IBs) in the ZnO grains and the IBs-induced grain-growth mechanism resulted in uniform grain growth and hence a microstructure with smaller ZnO grains and a narrower grain size distribution. The final phase composition of the samples prepared by the DMCP method mainly depended on the presence of varistor dopants that can prevent the formation of the pyrochlore phase, especially Cr₂O₃, while MCA can affect it mostly by providing a homogeneous distribution of those dopants. The DMCP varistor samples prepared with MCA had much better current–voltage characteristics than the samples of the same composition prepared from unactivated powders.     

High-current measurement of the grain resistivity in zinc oxide varistor ceramics

A new pulse technique for grain resistivity measurement in varistor ceramics is suggested. Such technique allows obtaining more precise value of the grain resistivity due to the use of the concept of differential electrical resistance. This technique can be used in the current density range where the overheating of varistor sample is insignificant. The technique was verified using commercial ZnO varistors. Grain resistivities of 0.60±0.02 Ω cm at 293 K and of 3.40±0.13 Ω cm at 77 K were obtained. This result indicates the negative temperature coefficient of grain resistance in ZnO varistor in the range (77–293) K. The contribution of the grain boundaries to the current–voltage characteristic of ZnO varistor is estimated on the basis of the measured grain resistivity and the current–voltage data. It is shown that the electrical conduction in ZnO varistor is controlled by grains if the current density exceeds approximately 1000 А сm⁻².     

The dielectric properties and optical propagation loss of c-axis oriented ZnO thin films deposited by sol–gel process

The c-axis oriented ZnO thin films were prepared on various substrates by sol–gel processes. The stability of solution was examined through solvent and stabilizer. The c-axis orientation and grain size of films were increased with increasing of heat treatment temperature. The optical propogation losses of ZnO films deposited SiO₂/Si(111) substrates were measured using end-coupling method. The losses result in the scattering of the interface of ZnO/SiO₂, and the ZnO grain. Dielectric constant and resistivity of thin films deposited on Pt/SiO₂/Si(111) substrates are, respectively, in the range of 7–13 and 1.7×10⁴9.8×10⁵Ω cm.     

Interface states and MWS polarization contributions to the dielectric response of low voltage ZnO varistor

The main purpose of this work is to study the dielectric response of commercial low voltage ZnO varistors by means of dielectric relaxation spectroscopy (DRS) and thermally stimulated depolarization currents (TSDC) in a wide temperature range. Four relaxation processes have been studied here and all of them demonstrate Cole-Davidson behaviour. The first two faster relaxation mechanisms are known processes in ZnO varistors and those are related to the ZnO bulk traps. The next one faster relaxation mechanism attributed to the MWS polarization which should be related to the intergranular Bi-rich microregions. The remaining slower relaxation mechanism is associated to the grain boundaries interfaces. Based on the block model for the ZnO varistor a gradual reduction in the total depletion width is observed at a temperature about 330 K, which can be considered that is due to the gradual decrease of the interface states density at this temperature region.     

Microstructure Development in Low-Antimony Oxide-Doped Zinc Oxide Ceramics

The grain growth of ZnO ceramics sintered with low additions of Sb₂O₃ (<500 ppm of Sb) was investigated. Additions of Sb<250 ppm resulted in a coarse-grained microstructure with large ZnO grains (55–70 μm), much larger than the grain size of ZnO ceramics without any Sb₂O₃ addition (45 μm). The addition of 500 ppm of Sb resulted in a fine-grained microstructure with an average ZnO grain size of about 12 μm. The results are explained by an inversion-boundary (IB) -induced grain-growth mechanism. The grain-growth exponent has a value of about 2 as long as the grains containing IBs grow at the expense of IB-free grains. It increases to about 4 after the IB-containing grains impinge on each other, and achieves values above 10 for additions of 500 ppm of Sb when IBs nucleate in nearly all the ZnO grains so that grains with IBs prevail in the microstructure at an early stage in the grain-growth process.     

Simultaneously improving the electrical properties and long-term stability of ZnO varistor ceramics by reversely manipulating intrinsic point defects

Excellent electrical properties and the improved long-term stability of ZnO varistor ceramics were simultaneously achieved by doping NiO. The microstructural features were investigated using X-ray diffractometer, scanning electron microscopy, and energy dispersive spectroscopy, while the intrinsic point defects were characterized using frequency domain dielectric spectroscopy and verified by photoluminescence and Raman spectra. The results indicated that in the ZnO varistor ceramics, a reverse manipulation of donor point defects, i.e., suppressing mobile zinc interstitial but increasing stable oxygen vacancy, was achieved. The long-term stability of NiO-doped ZnO ceramics was improved via a decrease in zinc interstitial density, with a degradation rate of 0.064 μA cm^?2 h^?0.5. Meanwhile, due to an increase in oxygen vacancy density, the excellent nonlinear current–voltage performance, i.e., a high nonlinear coefficient (72.9), low leakage current density (0.08 μA cm^?2), and low grain resistivity (13.43 × 10^?3 Ω m), was maintained. The findings of this study provide a possible method for developing high-performance ZnO varistor ceramics by manipulating point defects.     

Precoarsening to Improve Microstructure and Sintering of Powder Compacts

MgO and Al₂O₃ were sintered by two types of processes: a conventional isothermal sintering and a two-step sintering consisting of an initial low-temperature precoarsening treatment before conventional isothermal sintering. The final microstructure from two-step sintering can be more uniform and finer than that of compacts sintered conventionally. A narrow-size-distribution alumina powder was sintered under constant-heating-rate conditions, with and without a precoarsening treatment, and the results were compared. The differences between two-step and conventional processing were clarified by experiments on precoarsened and as-received ZnO powders. These compacts were precoarsened at 450°C for 90 h with virtually no increase in the overall density. The resulting grain size was 1.7 times the starting one, but the standard deviation of the precoarsened powder size distribution was smaller than that of the asreceived powder. Precoarsened compacts sintered to nearly full density showed improved homogeneity. The sintering stress of the precoarsened ZnO was approximately 0.8 that of the as-received one. A computational model has been used with two components of coarsening to describe the differences in pore spacing evolution between the precoarsened and the as-received system. The benefit of two-step sintering is attributed to the increase in uniformity resulting from precoarsening. The increased uniformity decreases sintering damage and allows the system to stay in the open porosity state longer, delaying or inhibiting additional coarsening (grain growth) during the final stage of densification. Two-step sintering is especially useful for nonuniform powder systems with a wide size distribution and is a simple and convenient method of making more uniform ceramic bodies without resorting to specialized powders or complicated heat schedules.     

Two-Step Sintering of Nanocrystalline ZnO Compacts: Effect of Temperature on Densification and Grain Growth

Two-step sintering (TSS) was applied on nanocrystalline zinc oxide (ZnO) to control the accelerated grain growth occurring during the final stage of sintering. The grain size of a high-density (>98%) ZnO compact produced by the TSS was smaller than 1 μm, while the grain size of those formed by the conventional sintering method was ∼4 μm. The results showed that the temperature of both sintering steps plays a significant role in densification and grain growth of the nanocrystalline ZnO compacts. Several TSS regimes were analyzed. Based on the results obtained, the optimum regime consisted of heating at 800°C (step 1) and 750°C (step 2), resulting in the formation of a structure containing submicrometer grains (0.68 μm). Heating at 850°C (step 1) and then at 750°C (step 2) resulted in densification and grain growth similar to the conventional sintering process. Lower temperatures, e.g., 800°C (step 1) and 700°C (step 2), resulted in exhaustion of the densification at a relative density of 86%, above which the grains continued to grow. Thermogravimetric analysis results were used to propose a mechanism for sintering of the samples with transmission electron micrographs showing the junctions that pin the boundaries of growing grains and the triple-point drags that result in the grain-boundary curvature.     

Analysis of Nanocrystalline and Microcrystalline ZnO Sintering Using Master Sintering Curves

Master sintering curves were constructed for dry-pressed compacts composed of either a nanocrystalline or a microcrystalline ZnO powder using constant heating rate dilatometry data and an experimentally determined apparent activation energy for densification of 268±25 and 296±21 kJ/mol, respectively. The calculated activation energies for densification are consistent with one another, and with values reported in the literature for ZnO densification by grain boundary diffusion. Grain boundary diffusion appears to be the single dominant mechanism controlling intermediate-stage densification in both the nanocrystalline and the microcrystalline ZnO during sintering from 65% to 90% of the theoretical density (TD). Based on both the consistency of the calculated activation energy as a function of density and the narrow dispersion of the sintering data about the master sintering curve (MSC) for the nanocrystalline ZnO, there is no evidence of either significantly enhanced surface diffusion or grain growth during sintering relative to the microcrystalline ZnO. The MSC constructed for the nanocrystalline ZnO was used to design time–temperature profiles to successfully achieve four different target sintered densities on the MSC, demonstrating the applicability of the MSC theory to nanocrystalline ceramic sintering. The most significant difference in sintering behavior between the two ZnO powders is the enhanced densification in the nanocrystalline ZnO powder at shorter times and lower temperatures. This difference is attributed to a scaling (i.e., particle size) effect.     

Effects of aluminium doping on structural and photoluminescence properties of ZnO nanoparticles

Structural and optical properties of Al doped ZnO nanoparticles prepared by the thermal decomposition method are presented. X-ray diffraction studies confirmed the substitution of Al on Zn sites without changing the hexagonal structure of ZnO. Also, lattice parameters, the crystallite size and other physical parameters such as strain, stress and energy density were calculated from various modified forms of W–H equation and their variation with the doping of Al is discussed. A blue shift in the energy band gap attributed to increase in carrier concentration (Burstein Moss Effect) is observed by absorption spectra. Photoluminescence studies show a strong and dominant peak corresponding to the near band edge emission in ultraviolet range and a broad band in the range 420–520 nm corresponding to defects and oxygen vacancies. Phonon modes were studied by FTIR measurements. The tunability of the band gap of ZnO nanoparticles could eventually be useful for potential optoelectronic applications.     

ZnO Agglomeration and Its Effect on the Preparation of a Mixture for Production of Varistors by a Dopant Deposition Method

A suspension mixture for production of ZnO-based varistors is prepared by a dopant deposition method. The effect of deposition conditions (ZnO concentration in the suspension and the use of a thinning agent) on the density, ZnO grain size, and electrical characteristics of ceramics prepared from the deposited suspensions is studied. Properties of ceramics prepared by the suspension method are compared to those of ceramics prepared by conventional methods.     

Fully Dense, Fine-Grained, Doped Zinc Oxide Varistors with Improved Nonlinear Properties by Thermal Processing Optimization

Fully dense, doped ZnO varistors were prepared using an easy two-stage pressureless-sintering method at temperatures as low as 825°C, with a grain size of ∼0.5 μm. After the highly nonohmic ZnO varistors were sintered, their fine microstructure consisted of uniformly sized grains, small spinel grains with partially dissolved manganese and cobalt oxides discontinuously distributed in the fairly wide grain boundaries, and an intergranular layer of bismuth-rich crystalline phase mainly detected at three or four ZnO grain junctions. There were twins near the middle of almost all the ZnO grains. The abnormally high nonlinear properties of the almost nanostructured varistors ( F _B≈ 6–8 kV/mm and α= 270) were attributed to a uniform and very fine microstructure, a high ZnO–ZnO grain direct contacts concentration, and a uniform hybrid layer substructure (grain boundaries and twin boundaries) with different (but probably accumulative) potential barriers.     

In-situ study of electrophoretic deposition of zinc oxide nanosheets and nanorods

In the present work, the effects of two different morphologies of zinc oxide nanoparticles (nanosheets and nanorods) were investigated by in-situ measurement of deposition weight, and current density. ZnO nanosheets and nanorods were synthesized by microwave-assisted method using co-surfactant route. The average thickness of obtained nanosheets, and the average diameter of nanorods were measured to be about 26 nm and 139 nm, respectively. ZnO films were obtained by electrophoretic deposition from suspension of nanoparticles in ethanol under different voltages. Results indicated that ZnO nanosheets tend to have greater deposition rate than ZnO nanorods under similar conditions. The compactness of the film obtained from nanosheet suspension was higher than the one obtained from nanorod suspension. However, the film obtained from ZnO nanorods displayed more uniformity at different voltages in comparison to the film obtained from ZnO nanosheets, which can be due to different active surface area, and also different way of motion under hydrodynamic forces in the suspension.     

Structural and optical studies on sol–gel derived ZnO thin films by excimer laser annealing

High-quality polycrystalline ZnO thin films were deposited onto alkali-free glasses at a temperature of 300°C in air ambience by combining sol–gel spin coating and KrF excimer laser annealing. The effects of laser irradiation energy density on the crystallization, microstructure, surface morphology, and optical transmittance of as-prepared ZnO thin films were investigated and compared to the results of thermally annealed ZnO thin films. The crystallinity level and average crystallite size of laser annealed ZnO thin films increased as laser energy density increased. The crystallinity levels and average crystallite size of excimer laser annealed (ELA) thin films were greater than those of the thermally annealed (TA) thin films. However, laser annealed thin films had abnormal grain growth when irradiation energy density was 175 mJ/cm². Experimental results indicated that the optimum irradiation energy density for excimer laser annealing of ZnO sol–gel films was 150 mJ/cm². The ELA 150 thin films had a dense microstructure, an RMS roughness value of 5.30 nm, and an optical band gap of 3.38 eV, close to the band gap of a ZnO crystal (3.4 eV).     

Synthesis and cathodoluminescence properties of porous wood (fir)-templated zinc oxide

Wood (fir)-templated ZnO with hierarchically porous structure has been successfully synthesized through a simple hydrothermal process. Morphology and porosity of the products were investigated by FESEM, TEM, and N₂ adsorption, respectively. The optical properties were measured by cathodoluminescence (CL) at room temperature. The morphologies of bulk and ground flake ZnO show an inheritance from the fir microstructure. Experimental results suggest that a higher calcination temperature will influence the grain size and porosity. The pore size decreases from 20 to 10 μm in the bulk ZnO, while increases from 50 nm to several micrometers in the flake ZnO when the calcination temperature changes from 600 to 1200 °C. CL spectra also show temperature-dependent properties at ultraviolet (UV) band and blue band. The intensity of visible emission originated from oxygen vacancies is proportional to the calcination temperature, while that of UV emission is inverse proportional due to quantum confinement effect.     

Effect of gas-timing technique on structure and optical properties of sputtered zinc oxide films

Zinc oxide thin films were prepared by the RF magnetron sputtering using a gas-timing technique whereby the flow of argon into the sputtering chamber was controlled by an on–off sequence. With this technique, polycrystalline ZnO thin films on glass substrates have been achieved without any thermal treatment of the substrate. In addition, the RF power and the gas-timing sequence can be fine-tuned to produce the hexagonal structure of ZnO thin films. X-ray diffraction (XRD) measurements confirm a (0 0 2) plane oriented wurtzite structure ZnO thin films. The optimized conditions for this hexagonal structure are an RF power of 30 W and an on–off gas-timing sequence of 50:2 s. The root mean square surface roughness of ZnO thin films measured by atomic force microscopy are in the range of 6.4–11.5 nm. The optical transmittance of ZnO thin films is over 85% in the visible range.     

Fabrication and Characterization of Pure and Pb-doped ZnO Thin Films Prepared by Sol–Gel and Dip-coeting Method

In this paper, undoped and Pb-doped ZnO thin films have been prepared by sol gel method and deposited on glass substrate using dip-coating technique. The structural, morphological, and optical properties of the films were investigated as a function of Pb doping. The results of the structural tests showed that these films are of a polycrystalline hexagonal structure with a preferred orientation in the (002) direction. The grain size values of Pb-doped films were lower than that of pure ZnO, but the strain and the dislocation density values inecrease with increase Pb doping ratio. The atomic force microscopy (AFM) images showed that the particle size and Root Mean Square (RMS) of ZnO decrease with increasing Pb doping. The optical band gap values were found to increase from (3.19 to 3.30 eV) and the Urbach energy decrease from (322 to 313 meV). PL spectra exhibit an increased amount of defects with increasing Pb, which leads to a red shift in the UV region.