Enhancement of electrical conductivity by Al-doped ZnO ceramic varistors

Zn_1−xAl_xO ceramic samples with various x values (0.00≤x≤0.20) are sintered in air at temperatures of 850 °C for 10 h and then quenched to room temperature. Structural, surface morphology and I-V characteristics of the samples are investigated using X-ray diffractometer (XRD), scanning electron microscope (SEM) and dc electrical measurements. It is found that addition of Al up to 0.05 does not influence the well-known peaks related to wurtzite structure of ZnO ceramics, and other unknown peaks could be formed above 0.05 of Al. The cell parameters of Al-doped samples are a little shorter than the undoped ZnO, and also the shape and size of grains are clearly affected. Average crystalline diameters, deduced from XRD analysis, are between 39.90 and 47.18 nm, which are 25 times lower than those obtained from SEM micrographs. Although breakdown field, nonlinear coefficient and barrier height are generally decreased by Al addition, the electrical conductivity is improved. These results are discussed in terms of the interaction mechanism between atoms of Al and Zn in both under and over-doped regions.     

Mechanical and magnetic properties of ZnO/Fe2O3 ceramic varistors

Mechanical and magnetic properties of the ZnO/Fe₂O₃ ceramic varistors have been examined by using mechanical analyzer, digital microhardness tester and vibrating sample magnetometer. The initial stress–strain behavior is found to be linear (elastic) then becomes nonlinear (plastic deformation) without reaching the failure limit up to the maximum available stress (0.07 MPa). The compressive elastic modulus varies between 0.2 and 0.8 MPa with Fe addition up to 0.50. Furthermore, an approximately monotonically linear decrease in VHN with increasing Fe content up to 50% has been observed for all applied loads, which closely resembles the behavior of the true hardness and the surface energy. The magnetic measurements revealed an antiferromagnetic to paramagnetic to transition for all Fe doped samples. The Fe free sample showed paramagnetic behavior down to 2 K. The Neel temperature moderately increased from 18 K at 0.05% Fe to 25 K at 0.5% Fe. The magnetization (M) versus applied magnetic field (H) did not reach saturation for all samples up to 9 Tesla. The saturated magnetization (per Fe contents) is low and found to decreases linearly at a rate of (−35 emu/g-Fe) in a clear manifestation of the strengthening of the antiferromagnetic exchange interaction with increasing Fe contents.     

Stoichiometric lanthanum chromite based ceramic interconnects with low sintering temperature

Ceramic interconnects for use in solid oxide fuel cells are expected to operate between 800∼1000 °C, sinter between 1400∼1500 °C to allow co-firing and meet a number thermal mechanical requirements. The perovskite type (ABO₃) lanthanum chromite based materials have emerged as a leading candidate that will meet these criteria by varying the composition on the A and B sites. A need therefore exists to determine this material's temperature dependent electrical and mechanical properties with respect to these site substitutions. In this investigation, oxide powders were prepared by the glycine-nitrate process. Ionic substitutions were carried out on A sites with calcium or strontium, and B sites with cobalt and aluminum, respectively. Only stoichiometric compositions were considered for the sake of stability. The powders and their sinterability were investigated by XRD, SEM, dilatometry and density measurements. The sintered materials were further examined by SEM, thermal expansion and electric conductivity measurements in order to elucidate the resulting microstructure, electrical and mechanical properties.     

Improvement of sintering,nonlinear electrical,and dielectric properties of ZnO-based varistors doped with TiO_2

The effects of TiO_2 on sintering and nonlinear electrical properties of(98.5-x)ZnO–0.5MnO_2–0.5Co_2O_3-0.5Bi_2O_(3–x)TiO_2(x = 0.3,0.5,0.7,0.9 mol%) ceramic varistors prepared by the ceramic technique are investigated in this work.The optimum sintering temperature of the prepared samples is deduced by determining the firing shrinkage and water absorption percentages.The optimum sintering temperature is found to be 1200℃,at which each of the samples shows a maximum firing shrinkage and minimum water absorption.Also minimum water absorption appears in a sample of x = 0.9 mol%.Higher sintering temperature and longer sintering time give rise to a reduction in bulk density due to the increased amount of porosity between the large grains of ZnO resulting from the rapid grain growth induced by the liquid phase sintering.The crystal size of ZnO decreases with increasing TiO_2 doping.The addition of TiO_2 improves the nonlinear coefficient and attains its maximum value at x = 0.7 mol% of TiO_2,further addition negatively affects it.A decrease in capacitance consequently in the dielectric constant is recorded with increasing the frequency in a range of 30 kHz–200 kHz.The temperature and composition dependences of the dielectric constant and AC conductivity are also studied.The increase of temperature raises the dielectric constant because it increases ionic response to the field at any particular frequency.     

Structural and electronic characteristics of pure and doped ZnO varistors

We report here the structural,surface morphology,mechanical,and current-voltage characteristics of Zn1-xMxO ceramic samples with various x and M(0.00≤x≤0.20,M=Ni,Cu).It is found that the considered dopants do not influence the well-known peaks related to the wurtzite structure of ZnO ceramics,while the shapes and the sizes of grains are clearly affected.The average crystalline diameters deduced from the SEM micrographs are between 2.06 μm and 4.8 μm for all samples.The oxygen element ratio is increased by both dopants.Interestingly,the potential barrier can be formed by adding Cu up to 0.20,while it is completely deformed by 0.025 Ni addition.The breakdown field can be enhanced up to 4138 V/cm by 0.025 Cu addition,followed by a decrease with further increase of Cu up to 0.20.On the other hand,a gradual decrease in Vickers microhardness is reported for both dopants,and the values in the Ni samples are higher compared to those in the Cu samples.The electrical conductivity is generally improved by Ni,while the addition of Cu improves it only in the over doped region(≥0.10).These results are discussed in terms of the differences of valency and ferromagnetic ordering.     

Correlation between electrical, optical properties and Ag centers of ZnO:Ag thin films

ZnO:Ag films have been fabricated on a n-Si (1 1 1) substrate and then annealed in situ in an O₂ ambient, using Ag₂O as a silver dopant by pulsed laser deposition. Hall measurements reveal that the films prepared at 400 and 450 °C show p-type behavior with a hole concentration of 6.3×10¹⁶–1.2×10¹⁷ cm^–3 and a mobility of 2.48–3.30 cm²/V s. By combining Hall measurements, electron paramagnetic resonance (EPR) signals, and photoluminescence (PL) spectra, a correlation is observed between the free hole carriers, the Ag²⁺ centers, and the neutral acceptor bound excitons. Additionally, the p-ZnO:Ag/n-Si heterojunction shows a diode-like I–V characteristic.     

Room temperature magnetic properties of ZnO nanostructured films

The ZnO nanorod array films have been epitaxially deposited on indium tin oxide (ITO) glass along 〈0001〉 direction. It is found that the film is grown in a two-step process including nanoparticle film nucleation and oriented rod growth. The as-prepared ZnO film shows a dominant diamagnetic signal and a weak ferromagnetic signal at room temperature. The room temperature ferromagnetism deteriorated by annealing in air or N₂. The photoluminescent spectra revealed that the intensity of ZnO defect band decreases after annealing. Thus, the decreased ferromagnetism is likely to have resulted from the decrease of oxygen vacancies and defects in the as-prepared film. Moreover, ZnO deposited at various times showed that defects located at or near the interface between the substrate and the film play a major role in ferromagnetism. It suggests that ferromagnetism can be tuned by changing the defects in ZnO.     

High temperature thermoelectric properties of Nb-doped ZnO ceramics

Solid-state reaction processing technique was used to prepare Zn_xNb_1−xO (0≤x≤0.02) polycrystalline bulk samples. In the present study, we find that their lattice parameters a and c tend to decrease with increasing amount of Nb additive. The electrical conductivity of all the Zn_1−xNb_xO samples increased with increasing temperature, indicating a semiconducting behavior in the measured temperature range. The addition of Nb₂O₅ to ZnO led to an increase in the electrical conductivity and a decrease in the absolute value of the Seebeck coefficient. The best performance at 1000 K has been observed for nominal 0.5 at% Nb-doped ZnO, with an electrical resistivity of about 73.13 (S cm⁻¹) and Seebeck coefficient of ∼257.36 μV K⁻¹, corresponding to a power factor (S²σ) of 4.84×10⁻⁴ Wm⁻¹ K⁻². The thermal conductivity, κ, of the oxide decreased as compared to pure ZnO. The figure of merit ZT values of ZnO-doped Nb₂O₅ samples are higher than the ZnO pure sample, demonstrating that the Nb₂O₅ addition is fairly effective for enhancing thermoelectric properties.     

Correlation of ZnO thin film surface properties with conductivity

Technological demands for the fabrication of nanostructured active coatings provide renewed motivation for understanding the properties that control the morphology of the thin film surface. With decreasing structure size, the issues of finite size and shape effects become non-negligible including issues of stability against decay and structural rearrangement. The surface of the wide band gap semiconductor ZnO is known to be very active, with a wide variety of absorption and chemisorptions phenomena taking place. These processes can alter the charge carrier distribution in the sub-surface region and locally change the doping levels. There is a limited amount of literature dedicated to systematic and detailed studies on the surface evolution with growth parameters and their effect on the ZnO surface conductivity under reduction/oxidation. Therefore, this work focuses on the analysis of the thin ZnO film surface properties by studying specific surface parameters such as amplitude related parameters (average roughness, the root mean square), mixed parameters (surface area ratio), functional parameters for characterizing bearing and fluid retention (skewness), and spatial parameters (the fractal dimensions) as they correlate with the film conductivity changes under subsequent exposure to UV light (as reductor factor) and ozone (as surface oxidant agent). All ZnO thin films of different thicknesses were grown by the dc planar magnetron sputtering technique under the same sputtering conditions. PACS 68.37.Ps; 73.25.+I; 73.50.-h; 73.50.Pz     

Correlation between green luminescence and morphology evolution of ZnO films

Photoluminescence and atomic force microscopy have been used to characterize ZnO thin films grown by metal-organic chemical vapor deposition (MOCVD) at varied growth pressures. The surface morphology with different grain structures has strong influence on the green photoluminescence of ZnO. When large discrete islands or structureless overgrowth cover the rough surface, broad green emissions around 500 nm go beyond the ultraviolet (UV) emission band; whereas, when the surface is packed closely with small grains, only weak green emission is observed with a red-shift to 528 nm. This variation of green emissions is ascribed to changes in the charge states of oxygen vacancies, which is strongly dependent on the surface morphology and grain structures. Based on the grain boundary defect model, two possible recombination processes for the green emission are proposed and discussed in detail. PACS 68.55.Jk; 78.55.Et; 81.05.Dz     

Correlation between electrical and optical properties of Cr:ZnO thin films grown by pulsed laser deposition

Highly transparent and conducting Chromium doped ZnO (Cr:ZnO) thin films with preferential c-axis orientation were grown on (0 0 0 1) sapphire substrates using buffer assisted pulsed laser deposition. The resistivity of Cr:ZnO thin films was found to decrease to a minimum value of ∼1.13×10⁻³Ω cm with the increasing Cr concentration up to ∼1.9 at.% and then increase with further increase of Cr concentration. On the contrary, the band gap and carrier concentration of Cr:ZnO thin films increased up to ∼3.37 eV and ∼2×10²⁰ cm⁻³, respectively, with the increase of Cr concentration up to ∼1.9 at.%, then decreased with further increase of Cr concentration. The increase of carrier concentration and conductivity with Cr doping at low Cr concentrations (<1.9 at.%) could be attributed to the presence of Cr in +3 valence state in ZnO thus acting as donor while decrease of carrier concentration beyond ∼1.9 at.% of Cr concentration could be attributed to the charge compensating effect due to the presence of acceptor like point defects such as oxygen interstitials. This was experimentally confirmed using x-ray photoelectron spectroscopy. The observed variation in the band gap of Cr:ZnO thin films with increasing Cr doping was attributed to the competing effects of the high free carrier concentration induced Burstein-Moss blue shift and band gap narrowing.     

Correlation between atomic size and elastic properties/glass transition temperature in metallic glasses

<正>As a relative newcomer in the glass family,metallic glass challenges our standpoint on crystalline metals and extends our knowledge concerning the nature of glasses[1].Metallic glasses have attracted considerable attention because of their unique mechanical,physical,and chemical properties[2-4].Newly developed bulk metallic glass can combine toughness and strength beyond the benchmark ranges established by the     

Correlation between Curie temperature and system dimension

Curie temperature T_C of spin arrangement with arbitrary dimension was considered. We assumed that interaction of a spin with all other spins vary with a power-law decay rate in exchange integral on Heisenberg model. As a result, we found that T_C, which was obtained from T_C=λC (λ: mean-field coefficient and C: Curie constant), significantly depends on fractal dimension of spin arrangements D, the exchange integral and the decay constant. This semi-quantitatively explains how T_C depends on D (1≤D≤3) in a universal way and also the finite size effect on T_C in low-dimensional spin systems.     

低温下单根ZnO纳米带电学性质的研究

用化学气相沉积法在硅衬底上合成了宽1 μm左右、长数十微米的ZnO纳米带. 采用微栅模板法得到单根ZnO纳米带半导体器件, 由I-V特性曲线测得室温下ZnO纳米带电阻约3 MΩ, 电阻率约0.4 Ω·cm. 研究了在20–280 K温度范围内单根ZnO纳米带电阻随温度的变化. 结果表明: 在不同温度区间内电阻随温度变化趋势明显不同, 存在两种不同的输运机制. 在130–280 K较高的温度范围内, 单根ZnO纳米带电子输运机制符合热激活输运机制, 随着温度继续降低(< 130 K), 近邻跳跃传导为主导输运机制. 关键词： ZnO 纳米带 低温 输运机制     

Influence of sintering temperature on properties of BNKLLT–6 wt% BCTZ binary lead-free piezoelectric ceramic prepared through the solid-state combustion technique

In this work, a new binary 94 wt%[Bi_0.5(Na_0.68K_0.22Li_0.1)_0.5TiO₃ + 0.10 wt% of La₂O₃]–6 wt% [(Ba_0.85Ca_0.15)(Ti_0.90Zr_0.10)O₃] [BNKLLT–6 wt% BCTZ] ceramic was fabricated by the solid-state combustion technique and glycine was used as the fuel. The effect of sintering temperature in the range of 1075–1175 °C for 2 h on phase evolution, microstructure and electrical properties was investigated. The phase formation exhibited a coexistence structure between rhombohedral and tetragonal at low sintering temperature. As the sintering temperature increased, the phase formation changed to pseudo-cubic phase. The average grain size of the ceramics was increased with the increasing sintering temperature. Density, ?_r, ?_SA and T_FA of BNKLLT–6 wt% BCTZ ceramics increased while the T_SA decreased when the sintering temperature increased up to 1125 °C, while after this temperature the opposite trends occurred. At a sintering temperature of 1125 °C, the BNKLLT-6 wt% BCTZ sample showed the highest theoretical density (95.8%), maximum dielectric constant ?_SA (5278), highest d₃₃ (227 pC/N) and fair ferroelectric properties (P_r = 24.5 µC/cm² and E_c = 15.45 kV/cm).     

Room temperature magnetic properties of Fe and C implanted ZnO films

ZnO films prepared by radio frequency magnetron sputtering were singly or sequentially implanted with 120 keV Fe ions at a fluence of 5 × 10¹⁶ ions/cm² and 20 keV C ions at a fluence of 3 × 10¹⁵ ions/cm². Magnetic and optical properties as well as structures of the films have been investigated using various techniques. Magnetic measurements show that the as-deposited ZnO film presents room temperature ferromagnetism. Single Fe or C ion implantation has no contribution to enhancement in the film magnetism, while magnetic moment increases distinctly in the Fe and C ions sequentially implanted film. Results from structural measurements reveal that Fe nanoparticles are formed in the Fe singly implanted ZnO film. The post C implantation induces dissolution of Fe nanoparticles and promotes Fe atoms to substitute Zn atoms in the lattice. Based on the structural results, the effect of magnetic enhancement has been tentatively interpreted.