Electrostatic force microscopy as a tool to estimate the number of active potential barriers in dense non-Ohmic polycrystalline SnO2 devices

In the present work, electroactive grain boundaries of highly dense metal oxide SnO2-based polycrystalline varistors were determined by electrostatic force microscopy (EFM). The EFM technique was applied to identify electroactive grain boundaries and thus estimate the amount of active grain boundary, which, in the metal oxide SnO2-based varistor, was calculated at around 85%, i.e., much higher than that found in traditional metal oxide ZnO-based varistors. The mean potential barrier height value obtained from the EFM analysis was in complete agreement with the values calculated from the C-V measurements, together with a complex capacitance plane analysis that validates the methodology proposed here. (c) 2006 American Institute of Physics.

Influence of simultaneous addition of MnO2 and CoO on properties of SnO2-based ceramics

This paper reports on a study of the: effect of replacing CoO by MnO2 on the sintering and electrical propel-ties of the 98.95% SnO2 + (1 - x)% CoO + x% MnO2 + 0.05% Ta2O5 system. All the samples were compacted into pellets and sintered at 1300 degrees C for 1 h, when they reached densities of about 98% of the theoretical density. An X-ray diffraction (XRD) analysis showed no other detectable phases other than SnO2. Current-voltage characterization indicated varistor behavior in the systems. The non-linear coefficient (alpha) and breakdown electric field (Eb) increased as the amount of MnO2 was increased. The results are explained in terms of an electric barrier modification, due to the presence of adsorbed negative oxygen species at the grain boundary inter face. (C) 2000 Elsevier B.V. B.V. All rights reserved.

Effect of atmosphere on the electrical properties of TiO2-SnO2 varistor systems

This work illustrates the advancement of research on TiO2-based electroceramics. In this work will be presented that the addition of different dopants, as well as thermal treatments at oxidizing and inert atmosphere, influences of the densification, the mean grain size and the electrical properties of the TiO2-based varistor ceramics. Dopants like Ta2O5, Nb2O5, and Cr2O3 have an especial role in the barrier formation at the grain boundary in the TiO2 varistors, increasing the nonlinear coefficient and decreasing the breakdown electric field. The influence of Cr'(Ti) is to increase the O' and O'(2) adsorption at the grain boundary interface and to promote a decrease in the conductivity by donating electrons to O-2 adsorbed at the grain boundary. In this paper, TiO2 and (Sn,Ti)O-2-based studies of polycrystalline ceramics, which show a non-linear I-V electrical response typical of low voltage varistor systems are also presented. All these systems are potentially promising for varistor applications. (C) 2004 Kluwer Academic Publishers.

Rietveld refinement, microstructure, conductivity and impedance properties of Ba[Zr0.25Ti0.75]O-3 ceramic

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Impedance spectroscopy analysis of TiO(2) thin film gas sensors obtained from water-based anatase colloids

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

The effect of TiO(2) on the microstructural and electrical properties of low voltage varistor based on (Sn,Ti)O(2) ceramics

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

SnO2, ZnO and related polycrystalline compound semiconductors: An overview and review on the voltage-dependent resistance (non-ohmic) feature

The present review describes mainly the history of SnO2-based voltage-dependent resistors, discusses the main characteristics of these polycrystalline semiconductor systems and includes a direct comparison with traditional ZnO-based voltage-dependent resistor systems to establish the differences and similarities, giving details of the basic physical principles involved with the non-ohmic properties in both polycrystalline systems. As an overview, the text also undertakes the main difficulties involved in processing SnO2- and ZnO-based non-ohmic systems, with an evaluation of the contribution of the dopants to the electronic properties and to the final microstructure and consequently to the system's non-ohmic behavior. However, since there are at least two review texts regarding ZnO-based systems [Levinson, L. M., and Philipp, H. R. Ceramic Bulletin 1985;64:639; Clarke, D. R. Journal of American Ceramic Society 1999;82:485], the main focus of the present text is dedicated to the SnO2-based varistor systems, although the basic physical principles described in the text are universally useful in the context of dense polycrystalline devices. However, the readers must be careful of how the microstructure heterogeneity and grain-boundary chemistry are capable to interfere in the global electrical response for particular systems. New perspectives for applications, commercialization and degradation studies involving SnO2-based polycrystalline non-ohmic systems are also outlined, including recent technological developments. Finally, at the end of this review a brief section is particularly dedicated to the presentation and discussions about others emerging non-ohmic polycrystalline ceramic devices (particularly based on perovskite ceramics) which must be deeply studied in the years to come, specially because some of these systems present combined high dielectric and non-ohmic properties. From both scientific and technological point of view these perovskite systems are quite interesting. (c) 2007 Elsevier Ltd. All rights reserved.

Optical emission and electron capture of rare-earth trivalent ions located at distinct sites in SnO(2) thin films

We present photoluminescence and decay of photo excited conductivity data for sol-gel SnO(2) thin films doped with rare earth ions Eu(3+) and Er(3+), a material with nanoscopic crystallites. Photoluminescence spectra are obtained under excitation with several monochromatic light sources, such as Kr(+) and Ar(+) lasers, Xe lamp plus a selective monochromator with UV grating, and the fourth harmonic of a Nd: YAG laser (4.65eV), which assures band-to-band transition and energy transfer to the ion located at matrix sites, substitutional to Sn(4+). The luminescence structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at grain boundary layer, where it is placed in asymmetric sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference between capture energy and grain boundary barrier is not so evident, even though the luminescence spectra are rather distinct.

Effect of atmosphere and dopants on sintering of SnO2

Tin oxide is an n-type semiconductor material with a high covalent behavior. Mass transport in this oxide depends on the surface state promoted by atmosphere or by the solid solution of a non-isovalent oxide doping The sintering and grain growth of this type of oxide powder is then controlled by atmosphere and by extrinsic oxygen vacancy formation. For pure SnO2 powder the surface state depends only on the interaction of atmosphere molecules with the SnO2 surface. Inert atmosphere like argon or helium promotes oxygen vacancy formation at the surface due to reduction of SnO2 to SnO at the surface and liberation of oxygen molecules forming oxygen vacancies. As consequence surface diffusion is enhanced leading to grain coarsening but no densification. Oxygen atmosphere inhibits the SnO2 reduction decreasing the surface oxygen vacancy concentration. Addition of dopants with lower valence at sintering temperature creates extrinsic charged oxygen vacancies that promote mass transport at grain boundary leading to densification and grain growth of this polycrystalline oxide.

Contribution of oxygen related defects to the electronic transport in SnO2 sol-gel films

SnO2 deposited by sol-gel is a polycrystalline film with small grain size. Oxygen present at a less grain boundary traps electrons and then the depletion layer around the potential barrier of the grain boundary becomes wider, comparable to the grain size. We have modeled the conductivity taking into account the trapped charge at the depletion layer of the grain boundary and other scattering mechanisms such as ionized impurity and polar optical. Experimental data of photoconductivity of SnO2 sol-gel films are simulated considering the dominant scattering at grain boundary and crystallite bulk. The fraction of trapped charge at the grain boundary depends on temperature and wavelength of irradiating light, being as high as 50% for illumination in the range 500-600 nm for SnO2-2%Nb as grown sample annealed in air to 550°C. This fraction can be quite reduced depending on exposure to light and annealing under different oxygen partial pressure conditions.

Effect of atmosphere and dopants on sintering of SnO2

Tin oxide is an n type semiconductor material with a high covalent behavior. Mass transport in this oxide depends on the surface state promoted by atmosphere or by the solid solution of aliovalent oxide doping. The sintering and grain growth of this type of oxide powder is then controlled by atmosphere and by extrinsic oxygen vacancy formation. For pure SnO2 powder the surface state depends only on the interaction of atmosphere molecules with the SnO2 surface. Inert atmosphere like argon or helium promotes oxygen vacancy formation at the surface due to reduction of SnO2 to SnO at the surface and liberation of oxygen molecules forming oxygen vacancies. As a consequence surface diffusion is enhanced leading to grain coarsening but no densification. Oxygen atmosphere inhibits SnO2 reduction by decreasing the surface oxygen vacancy concentration. Addition of dopants with lower valence at the sintering temperature creates extrinsic charged oxygen vacancies that promote mass transport at the grain boundary leading to densification and grain growth of this polycrystalline oxide.

Microstructure of doped barium titanate prepared from polymeric precursors

Barium titanate is used extensively as a dielectric in ceramic capacitors, particularly due to its high dielectric constant and low dielectric loss characteristics. It can be made semiconducting by addition of certain dopants and by proper modification of grains and grain boundary properties obtaining very interesting characteristics for various applications. The synthesis method and sintering regime have a strong influence on properties of obtained barium titanate ceramics. Doped barium titanate was prepared with Nb+5 and Y+3 ions as donor dopants, and with Mn+2 ions as acceptor dopant by polymeric precursors method. By this procedure nanosized powders were obtained after calcination. Sintering was performed in the temperature range of 1290°C to 1380°C The microstructure of doped BaTiO3 was performed using scanning electron microscopy. The influence of dopants and sintering temperature on grain size was analysed.

Ceramic Crucible Corrosion by Heavy Metal Oxide Glasses, Part II: Diffusion Study

Due to their low cost and high resistance to corrosion, ceramic crucibles can be used for the melting of PBG glasses (PbO-BiO 1.5GaO 1.5). These glasses present good window transmission from ultra-violet to infrared, making their use as optical fibres promising. However, their disadvantage is the high reactivity, leading to the corrosion of different crucibles, including gold and platinum ones. In this work, the corrosion of Al 2O 3, SnO 2 and ZrO 2 crucibles after melting at temperatures varying from 850 to 1000°C, was evaluated by Scanning Electronic Microscopy (SEM) in conjunction with microanalysis by EDS. The lead diffusion profile in the crucible material was obtained. Diffusion coefficients were calculated according to the Fick and Fisher theories. Results indicated that the different crucibles presented similar behaviour: in the region near the interface, diffusion occurs in the volumetric way and in regions away from the interface, diffusion occurs through grain boundary.

Degradación y recuperación de varistores de ZnO

In the present work it was studied the main aspect that influences on degradation and physical-chemical properties at grain-boundary region of metal oxide varistors and its consequences on microstructure and nonohmic electric properties. Based on the comprehension of the degradation aspects it was proposed some methodologies to recover the varistors nonohmic properties after being failed with long (2000 μs) and short current pulses (8/20 μs). Our analysis shown that one of the cause of degradation process is related to the lowering of oxygen species amount at grain-boundary region. Therefore, it is possible to re-promote oxygen enrichment of such regions by specific thermal treatments in rich oxygen atmospheres (the best condition found in the present work was temperatures around 900°C for 2 h at an oxygen flux of 15 1/h). The proposed nonohmic properties recovering procedure appear to be valid for all kind metal oxide varistors studied and is very important from technological point of view.

Optical and transport properties of rare-earth trivalent ions located at different sites in sol-gel SnO2

Photoluminescence and photo-excited conductivity data as well as structural analysis are presented for sol-gel SnO2 thin films doped with rare earth ions Eu3+ and Er3+, deposited by sol-gel-dip-coating technique. Photoluminescence spectra are obtained under excitation with various types of monochromatic light sources, such as Kr+, Ar+ and Nd:YAG lasers, besides a Xe lamp plus a selective monochromator with UV grating. The luminescence fine structure is rather different depending on the location of the rare-earth doping, at lattice symmetric sites or segregated at the asymmetric grain boundary layer sites. The decay of photo-excited conductivity also shows different trapping rate depending on the rare-earth concentration. For Er-doped films, above the saturation limit, the evaluated capture energy is higher than for films with concentration below the limit, in good agreement with the different behaviour obtained from luminescence data. For Eu-doped films, the difference in the capture energy is not so evident in these materials with nanoscocopic crystallites, even though the luminescence spectra are rather distinct. It seems that grain boundary scattering plays a major role in Eu-doped SnO2 films. Structural evaluation helps to interpret the electro-optical data. © 2010 IOP Publishing Ltd.