Influence of thermal annealing treatment in oxygen atmosphere on grain boundary chemistry and non-ohmic properties of SnO2 center dot MnO polycrystalline semiconductors

The present work studied the influence of thermal treatment in oxygen rich atmosphere on heterogenous junctions in Mn-doped SnO2 polycrystalline system presenting varistor behavior. The samples were prepared by conventional oxide mixture methodology, and were submitted to heat treatment in oxygen rich atmosphere at 900 degrees C for 2h. The samples were characterized by X-ray diffraction, scanning electron microscopy, dc and ac electrical measurements. The results showed that there is an evident relationship between the microstructure heterogeneity and non-ohmic electrical properties. It was found that for this SnO2 center dot MnO-based varistor system the heat treatment in oxygen rich atmosphere does not necessarily increase the varistors properties, which was related to the decrease in the grain boundary resistance. The results are compared with Co-doped SnO2 varistors and ZnO based varistors. (C) 2008 WILEY-VCH Verlay GmbH & Co. KGaA, Weinheim.

Relationship between grain-boundary capacitance and bulk shallow donors in SnO2 polycrystalline semiconductor

The relationship between grain-boundary capacitance and extrinsic shallow donors caused by Nb addition to SnO2 center dot COO binary polycrystalline system has been investigated by means of combined techniques such as I-V characteristic response, complex impedance and capacitance analysis and electrostatic force microscopy. The estimated role of the Nb doping is to increase the concentration of shallow donors that are capable of enhancing the electronic donation to grain-boundary acceptors. This effect leads to the formation of potential barriers at grain boundaries with a simultaneous increase of grain-boundary capacitance and non-Ohmic features of the polycrystalline device doped with Nb atoms.

Grain-boundary segregation and precipitates in La2O3 and Pr2O3 doped SnO2 center dot CoO-based varistors

Structural heterogeneities in SnO2.CoO-based varistors were analyzed by transmission electron microscopy. In SnO2.CoO-based system doped with La2O3 and Pr2O3 two kinds of precipitate phases at grain boundary region were found. Using energy dispersive spectrometry they were found to be Co2SnO4 and Pr2Sn2O7, presenting a defined crystalline structure. It was also identified that such precipitate phases are mainly located in triple-junctions of the microstructure. HRTEM analysis revealed the existence of other two types of junctions, one as being homo-junctions of SnO2 grains and other due to twin grain boundaries inside the SnO2.CoO grain. The role of these types of junction in the overall nonlinear electrical features is also discussed. (C) 2003 Elsevier B.V. Ltd. All rights reserved.

Grain boundary electric characterization of Zn7Sb2O12 semiconducting ceramic: A negative temperature coefficient thermistor

The electrical properties of the grain boundary region of electroceramic sensor temperature based on inverse spinel Zn7Sb2O12 were investigated at high temperature. The zinc antimoniate was synthesized by a chemical route based on the modified Pechini method. The electric properties of Zn7Sb2O12 were investigated by impedance spectroscopy in the frequency range from 5 Hz to 13 MHz and from 250 up to 600 degreesC. The grain boundary conductivity follows the Arrhenius law, with two linear branches of different slopes. These branches exhibit activation energies with very similar values; the low-temperature (less than or equal to350 degreesC) and high-temperature (greater than or equal to400 degreesC) regions are equal to 1.15 and 1.16 eV, respectively. Dissimilar behavior is observed on the relaxation time (tau) curve as a function of temperature, where a single slope is identified. The negative temperature coefficient parameters and nature of the polarization phenomenon of the grain boundary are discussed. (C) 2003 American Institute of Physics.

Temperature dependence of fractal dimension of grain boundary region in SnO2 based ceramics

Fractal dimensions of grain boundary region in doped SnO2 ceramics were determined based on previously derived fractal model. This model considers fractal dimension as a measure of homogeneity of distribution of charge carriers. Application of the derived fractal model enables calculation of fractal dimension using results of impedance spectroscopy. The model was verified by experimentally determined temperature dependence of the fractal dimension of SnO2 ceramics. Obtained results confirm that the non-Debye response of the grain boundary region is connected with distribution of defects and consequently with a homogeneity of a distribution of the charge carriers. Also, it was found that C-T-1 function has maximum at temperature at which the change in dominant type of defects takes place. This effect could be considered as a third-order transition.

Ferroelectric state analysis in grain boundary of Na0.85Li0.15NbO3 ceramic

The electric and dielectric properties of the grain boundary of Na0.85Li0.15NbO3 lead-free ferroelectric-semiconductor perovskite were investigated. The impedance spectroscopy was carried out as a function of a thermal cycle. The sodium lithium niobate was synthesized by a chemical route based on the evaporation method. Dense ceramic, relative density of 97%, was prepared at 1423 K for 2 h in air atmosphere. ac measurements were carried out in the frequency range of 5 Hz-13 MHz and from 673 to 1023 K. Theoretical adjust of the impedance data was performed to deriving the electric parameters of the grain boundary. The electric conductivity follows the Arrhenius law, with activation energy values equal to 1.55 and 1.54 eV for heating and cooling cycle, respectively. The nonferroelectric state of the grain boundary and its correlation with symmetry are discussed in the temperature domain. (C) 2003 American Institute of Physics.

Structural Characterization of Nanocrystalline Sb-Doped SnO2 Xerogels by Multiedge X-ray Absorption Spectroscopy

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Schottky emission in nanoscopically crystallized Ce-doped SnO2 thin films deposited by sol-gel-dip-coating

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Schottky-type grain boundaries in CCTO ceramics

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

Grain size effect on the electrical response of SnO2 thin and thick film gas sensors

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

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.

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.

Fractal approach to ac impedance spectroscopy studies of ceramic materials

A novel fractal model for grain boundary regions of ceramic materials was developed. The model considers laterally inhomogeneous distribution of charge carriers in the vicinity of grain boundaries as the main cause of the non-Debye behaviour and distribution of relaxation times in ceramic materials. Considering the equivalent circuit the impedance of the grain boundary region was expressed. It was shown that the impedance of the grain boundary region has the form of the Davidson-Cole equation. The fractal dimension of the inhomogeneous distribution of charge carriers in the region close to the grain boundaries could be calculated based on the relation ds = 1 + β, where β is the constant from the Davidson-Cole equation.

Decay of photo-induced conductivity in Sb-doped SnO2 thin films, using monochromatic light of about bandgap energy

Doping tin dioxide (SnO2) with pentavalent Sb5+ ions leads to an enhancement in the electrical conductivity of this material, because Sb5+ substitutes Sn4+ in the matrix, promoting an electronic density increase in the conduction band, due to the donor-like nature of the doping atom. Results of computational simulation, based on the Density Functional Theory (DFT), of SnO2:4%Sb and SnO2:8%Sb show that the bandgap magnitude is strongly affected by the doping concentration, because the energy value found for 4 at%Sb and 8 at%Sb was 3.27 eV and 3.13 eV, respectively, whereas the well known value for undoped SnO2 is about 3.6 eV. Sb-doped SnO2 thin films were obtained by the sol-gel-dip-coating technique. The samples were submitted to excitation with below theoretical bandgap light (450 nm), as well as above bandgap light (266 nm) at low temperature, and a temperature-dependent increase in the conductivity is observed. Besides, an unusual temperature and time dependent decay when the illumination is removed is also observed, where the decay time is slower for higher temperatures. This decay is modeled by considering thermally activated cross section of trapping centers, and the hypothesis of grain boundary scattering as the dominant mechanism for electronic mobility. © 2012 Elsevier B.V. All rights reserved.

Effect of yttrium doping in barium zirconium titanate ceramics: A structural, impedance, modulus spectroscopy study

In the current article, we studied the effect of yttrium [Y3+] ions' substitution on the structure and electric behavior of barium zirconate titanate (BZT) ceramics with a general formula [Ba1-x Y 2x/3](Zr0.25Ti0.75)O3 (BYZT) with [x = 0, 0.025, 0.05] which were prepared by the solid-state reaction method. X-ray diffraction patterns indicate that these ceramics have a single phase with a perovskite-type cubic structure. Rietveld refinement data confirmed [BaO 12], [ZrO6], [TiO6], [YO6] clusters in the cubic lattice. The Y3+ ions' effects on the electric conductivity behavior of BZT ceramics as a function of temperature and frequency are described, which are based on impedance spectroscopy analyses. The complex impedance plots display a double semicircle which highlights the influences of grain and grain boundary on the ceramics. Impedance analyses showed that the resistance decreased with the increasing temperature and resulted in a negative temperature coefficient of the resistance property in all compositions. Modulus plots represent a non-Debye-type dielectric relaxation which is related to the grain and grain boundary as well as temperature-dependent electric relaxation phenomenon and an enhancement in the mobility barrier by Y3+ ions. Moreover, the electric conductivity increases with the replacement of Ba 2+ by Y3+ ions may be due to the rise in oxygen vacancies. © 2013 The Minerals, Metals & Materials Society and ASM International.