The role of oxygen vacancies on the microstructure development and on the electrical properties of SnO2-based varistors

Variations on the microstructure development and on the electrical properties of SnO2-based varistors are discussed on the basis of the oxygen vacancies created or annihilated by the presence of different additives. Electron paramagnetic resonance (EPR) analysis of sintered samples evidenced a substantial increase in the paramagnetic oxygen vacancies concentration when Nb2O5 is added to the SnO2 center dot Co3O4 system. on the other hand, the observed diminution in the concentration of such species after the addition of Fe2O3 indicates solid solution formation. The quantification of paramagnetic oxygen vacancies allowed to confirm the proposed substitutions taking place in the lattice during sintering. These findings are supported by scanning electron microscopy, by density measurements and by current density versus electric field curves. The characterization of secondary phases through EDS assisted SEM and TEM is also reported in this work.

Structural and microstructural behaviour of SnO2 dense ceramics doped with ZnO and WO3

SnO2-based varistors doped with ZnO and WO3 were prepared by mixed oxide method. Experimental evidence shows that the increase in ZnO amount increases the volume and microstrain of unit cell while the WO3 promotes a decrease. The effect of ZnO and WO3 additives could be explained by the substitution of Sn4+ by Zn2+ and W6+. The addition of WO3 inhibits the grain growth due to the segregation in the grain boundary without influence in the densification of the samples. Besides that, an increase in the electrical resistance of the SnO2-ZnO-WO3 system was observed independent of the WO3 concentration. (c) 2005 Elsevier B.V. All rights reserved.

How Cr2O3 influences the microstructure and nonohmic features of the SnO2(COx, Mn1-x)O-based varistor system

An investigation was made to discover how the addition of Cr2O3 affects the microstructural heterogeneity and nonohmic features of the SnO2(Co-x, Mn1-x)O-based varistor system, with x varying from 0 to 1. The presence of Cr2O3 was found to strongly increase the nonohmic features when x = 1. However, the nonohmic features of the system decrease when x drops from 1 to 0, a behavior explained by the increase of the junction heterogeneity within the system's microstructure. accompanied by ail excess of precipitates at the triple point in the grain boundary region due to modified MnO sintering. The presence of these precipitates causes the leakage current to increase in response to the creation of ail ineffective barrier. The effect produced by heat-treating these systems in oxygen- and nitrogen-rich atmospheres suggests that, according to mechanisms previously discussed in the literature, Cr2O3 is more susceptible to oxygen, so that increasing the amount of oxygen in the grain boundary region may improve the system's nonohmic properties. (c) 2005 Elsevier Ltd. All rights reserved.

Electrical characterization of SnO2 : Sb ultrathin films obtained by controlled thickness deposition

A representative study is reported on the electrical properties of SnO2: Sb. ultrathin films (thickness of 40-70 nm) produced by a deposition method based on aqueous colloidal suspensions of 3-5 nm crystalline oxides. The results revealed the films' electrical behavior in a range of 10-300 K, showing a strong dependence on dopant incorporation, with minimum resistivity values in 10 mol % of Sb content. All the samples displayed semiconductor behavior, but the transport mechanism showed a strong dependence on thickness, making it difficult to fit it to well-known models. In thicker films, the mechanism proved to be an intermediary system, with thermally activated and hopping features. Electron hopping was estimated in the range of 0.4-1.9 nm, i.e., in the same order as the particle size. (c) 2007 American Institute of Physics.

Isothermal structural evolution of SnO2 monolithic porous xerogels

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Enhanced electrical property of nanostructured Sb-doped SnO2 thin film processed by soft chemical method

The effect of the Sb addition on the microstructural and electrical conductivity of the SnO2 thin film was studied in this work. Experimental results show that the Sb addition allowed to control the grain size and electrical conductivity of the SnO2 thin film, resulting in a nanostructured material. The nanostructured Sb-doped SnO2 thin films present high electrical conductivity, even in the presence of high porosity, supporting the hypothesis that nanostructured material must possess strong electrical conductivity. This work involves important aspects that can be applied to the development of high performance transparent conducting thin film. (C) 2003 Elsevier B.V. All rights reserved.

Solid-state and solution structural study of acetylacetone-modified tin(IV) chloride used as a precursor of SnO2 nanoparticles prepared by a sol-gel route

The effect of addition of different amounts of acetylacetone (acacH) on the species formed at room temperature and after thermohydrolysis at 70 degreesC for 30 and 120 min of ethanolic SnCl4.5H(2)O solutions is followed by EXAFS spectroscopy at the Sn K-edge. We show that thermohydrolyzed solutions are a mixture of SnO2 nanoparticles and soluble tin polynuclear species. The complexation of the tin molecular precursors by acetylacetonate ligands is evidenced by H-1, C-13, and Sn-119 NMR spectroscopy and EXAFS for a acacH/Sn ratio higher than 2. Single crystals are isolated from solution and the structure, determined by X-ray diffraction, is built up from monomeric Cl-3(H2O)Sn(acac)-H2O units bridged together by hydrogen bonding. The acacH/Sn ratio in solution controls the polycondensation of the hydrolyzed species but not the crystallite size of the SnO2 nanoparticles (similar to2 nm). Because of the major presence of chelated tin mono- and dimeric complexes in solution for acacH/Sn > 2, the condensation is almost inhibited, meanwhile the decrease of amount of chelated complexes for the acacH/Sn < 2 gives rise to an increase of the number of nanoparticles.

Drude's model calculation rule on electrical transport in Sb-doped SnO2 thin films, deposited via sol-gel

The evaluation of free carrier concentration based on Drude's theory can be performed by the use of optical transmittance in the range 800-2000 nm (near infrared) for Sb-doped SnO2 thin films. In this article, we estimate the free carrier concentration for these films, which are deposited via sol-gel dip-coating. At approximately 900 mn, there is a separation among transmittance curves of doped and undoped samples. The plasma resonance phenomena approach leads to free carrier concentration of about 5 x 1020 cm(-3). The increase in the Sb concentration increases the film conductivity; however, the magnitude of measured resistivity is still very high. The only way to combine such a high free carrier concentration with a rather low conductivity is to have a very low mobility. It becomes possible when the crystallite dimensions are taken into account. We obtain grains with 5 nm of average size by estimating the grain size from X-ray diffraction data, and by using line broadening in the diffraction pattern. The low conductivity is due to very intense scattering at the grain boundary, which is created by the presence of a large amount of nanoscopic crystallites. Such a result is in accordance with X-ray photoemission spectroscopy data that pointed to Sb incorporation proportional to the free electron concentration, evaluated according to Drude's model. (c) 2006 Elsevier Ltd. All rights reserved.

Anisotropic growth of oxide nanocrystals: Insights into the rutile TiO2 phase

In this work, we report the synthesis of titanium oxide nanocrystals, especially the rutile TiO2 phase with nanorod morphology, by a method based on peroxotitanium complex decomposition. The results indicate that the anisotropic morphology reported for rutile TiO2 nanocrystals is related to the oriented attachment process. Despite the predominance of rutile nanocrystals at longer treatment times, the nanocrystals were obtained also in the anatase type, according to the degradation time adopted. XANES results evidenced the absence of structural correlation between the peroxytitanium complex and phase evolution, and the coexistence of the two phases strongly suggests a correlation of the oriented attachment mechanism and the rutile phase stabilization.

Decay of photo-excited conductivity of Er-doped SnO2 thin films

Er-doped SnO2 thin films, obtained by sol-gel-dip-coating technique, were submitted to excitation with the 4th harmonic of a Nd:YAG laser (266 nm), at low temperature, and a conductivity decay is observed when the illumination is removed. This decay is modeled by considering a thermally activated cross section of an Er-related trapping center. Besides, grain boundary scattering is considered as dominant for electronic mobility. X-ray diffraction data show a characteristic profile of nanoscopic crystallite material (grain average size approximate to 5 nm) in agreement with this model. Temperature dependent and concentration dependent decays are measured and the capture barrier is evaluated from the model, yielding 100 meV for SnO2:0.1% Er and 148 meV for SnO2:4% Er.

The influence of sintering process and atmosphere on the non-ohmic properties of SnO2 based varistor

The non-ohmic properties of the 98.95% SnO2 + 1.0 CoO + 0.05 Nb2O5 (all in mole%) system, as well as the influence of sintering temperature and atmosphere on these properties, were characterized in this study. The maximum non-linear coefficient (alpha = 32) was obtained for a sintering temperature of 1300 degrees C in an oxygen atmosphere and this maximum is associated with the presence of O in SnO2 grain boundaries, as interface defects. Experimental results also indicate thermionic-type conduction mechanisms, which are associated with the potential barrier of Schottky or Poole-Frenkel types.

Influence of Ta2O5 on the electrical properties of ZnO- and CoO-doped SnO2 varistors

SnO2-based varistors doped with 0.5% cobalt, 0.5% zinc and various tantalum amounts were prepared by the solid-state route. Experimental evidence shows that small quantities of Ta2O5 improve the nonlinear properties of the samples significantly. It was found that samples doped with 0.05 mol% Ta2O5 exhibit the highest density (98.5%), the lowest electric breakdown field (E-b = 1050 V/cm) and the highest coefficient of nonlinearity (alpha = 11.5). The effect of Ta2O5 dopant could be explained by the substitution of Ta5+ by Sn4+. (C) 2004 Elsevier Ltd and Techna S.r.l. All rights reserved.

Poole-Frenkel effect in Er doped SnO2 thin films deposited by sol-gel-dip-coating

Electrical properties of Er-doped SnO2 thin films obtained by sol-gel-dip-coating technique were measured. When compared to undoped tin dioxide, rare-earth doped films present much higher resistivity, indicating that Er3+ presents an acceptor-like character into the matrix, which leads to a high degree of electric charge compensation. Current-voltage characteristics, measured above room temperature for Er-doped films, lead to non-linear behavior and two conduction regimes. In the lower electric field range the conduction is dominated by Schottky emission over the grain boundary potential barrier, which presents an average value of 0.85 eV. Increasing the applied bias, a second regime of conduction is observed, since the Poole-Frenkel coulombic barrier lowering becomes a significant effect. The obtained activation energy for ionization is 0.67 eV. (C) 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.