Improved Conductivity Induced by Photodesorption in SnO2 Thin Films Grown by a Sol-Gel Dip Coating Technique

Thin films of undoped and Sb-doped SnO2 have been prepared by a sol-gel dip-coating technique. For the high doping level (2-3 mol% Sb) n-type degenerate conduction is expected, however, measurements of resistance as a function of temperature show that doped samples exhibit strong electron trapping, with capture levels at 39 and 81 meV. Heating in a vacuum and irradiation with UV monochromatic light (305 nm) improve the electrical characteristics, decreasing the carrier capture at low temperature. This suggests an oxygen related level, which can be eliminated by a photodesorption process. Absorption spectral dependence indicates an indirect bandgap transition with Eg ≅ 3.5 eV. Current-voltage characteristics indicate a thermionic emission mechanism through interfacial states.

Oxygen related defects excitation and photoconductivity dependence of SnO2 sol-gel films with several light sources

Since oxygen vacancies act as donors in SnO2, the electrical properties are related to deviation from stoichiometric composition. Depending on stoichiometry SnO2 can be highly insulating or may exhibit fairly high n-type conductivity. Since bandgap transitions are in the ultraviolet range, its photoconductivity is strongly dependent on the excitation source. We have measured variation of photoconductivity excitation with wavelength for tin dioxide grown by dip-coating sol-gel technique using several light sources: tungsten lamp, xenon, mercury and deuterium, and present selected results. The main band is obtained in the range 3-4eV according to light source spectrum in the ultraviolet range. The presence of oxygen in the cryostat also affects the spectrum since electron-hole pairs react with adsorbed oxygen specimens. © 1999 OPA (Overseas Publishers Association) N.V. Published by license under the Gordon and Breach Science Publishers imprint.

Evolution of the viscoelastic properties of SnO2 colloidal suspensions during the sol-gel transition

This paper describes the effect of the concentration of electrolyte and pH on the kinetics of aggregation and gelation processes of SnO2 colloidal suspensions. Creep, creep-recovery, and oscillatory rheological experiments have been done in situ during aggregation and gelation. A phenomenological description of the structure of the colloidal system is given from the time evolution of rheological parameters. The dependence of the equilibrium steady-state shear compliance on the terminal region of clusters or aggregates seems to be a way to determine the beginning of interconnection of aggregates and the gel point. We propose that at this point the equilibrium steady-state compliance is a minimum. The steady-state viscosity determined from creep experiment can be fit with a power law with the extent of the transformation, giving critical exponent s = 0.7 ± 0.1. The value of the critical exponent Δ = 0.78 ± 0.05 was determined from oscillatory experiment. These results indicate that gelation of SnO2 colloidal suspension exhibits the typical scale expected from the scalar percolation theory. © 2000 Elsevier Science B.V. All rights reserved.

Effect of powder milling and dopant addition on the current-voltage characteristics of SnO2-based ceramics

Non-linear electrical properties of SnO2-based ceramics were investigated as a function of powder agglomeration condition and as a function of dopant addition. All doped powders presented a single phase, cassiterite, as evidenced by X-ray diffraction analysis. The effect of milling was quite evident, with non-milled powder showing higher agglomerated particle size than milled powder. Cr addition seemed to increase the non-linear coefficient. Cu and Mn rendered dense ceramics, but α values for systems with Mn were higher than for systems with Cu.

MnO2 influence on the electrical properties of SnO2-based ceramic systems

Tin dioxide is an n-type semiconductor that when doped with other metallic oxides exhibits non-linear electric behavior with high non-linear coefficient values typical of a varistor. In this work, electrical properties of the SnO2.CoO.Ta2O5 and SnO2.CoO.MnO2.Ta2O5 ceramics systems were studied with the objective of analyzing the influence of MnO2 on sintering behavior and electrical properties of these systems. The compacts were prepared by powder mixture process and sintered at 1300°C for 1 hour, in air, using a constant heating rate of 10°C/min. The morphological and structural properties were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The densities of the sintered ceramics were measured using the Archimedes method. The SnO2.CoO.Ta2O5 and SnO2.CoO.MnO2.Ta2O5 systems presented breakdown fields (Eb) about 3100 V.cm-1 and 3800 V.cm-1, respectively, and non-linear coefficient (α) about 10 and 20, respectively.

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.

Spectroscopic studies of SnO2 doped with Cr, Co or Nb

SnO2 ceramics doped with different amounts of Co, Cr or Nb were investigated using visible and infrared spectroscopy at room temperature. Based on the observed d-d transitions the valence states of incorporated dopants were determined. Values of the optical band-gap were calculated in all samples. The infrared spectra of the samples displayed variations in the position, relative intensity and width of the bands, which were attributed to the presence of dopants.

Métodos químicos para obtener varistores basados en SnO2

Synthesis of SnO2 ceramic powders was made by coprecipitation method and polymeric precursor method (Pechini) to obtain Sn-Co-Nb-Ti-Al varistor systems. The particles of the obtained ceramic powder presented nanometric size and SnO2 was the principal crystalline phase in them according to X-ray diffraction results. To determine the behavior of the synthesized samples in front of the thermal treatments, thermal analysis (DTA/TG) were made. Dilatometric studies on previously pressed samples were carried out. The optimal conditions of sintering of this raw material were determined. Microstructures and electric properties of sintered samples were studied using scanning electron microscopy (SEM) and I-V characteristics curves. The samples presented varistor behavior independent of the synthesis method used, with high nonlinearity values as 32. The presence of Al3+ favored the concentration of oxygen vacancies, and the grain growth.

Strain relaxation and stress-driven interdiffusion in InAsInGaAsInP nanowires

The authors have investigated strain relaxation in InAsInGaAsInP nanowires (NW's). Transmission electron microscopy images show an additional stress field attributed to compositional modulation in the ternary layer, which disrupts NW formation and drives Ga interdiffusion into InAs, according to grazing incidence x-Ray diffraction under anomalous scattering conditions. The strain profile along the NW, however, is not significantly affected when interdiffusion is considered. Results show that the InAs NW energetic stability is preserved with the introduction of ternary buffer layer in the structure. © 2007 American Institute of Physics.

Respuesta eléctrica de películas gruesas del sistema SnO2-TiO2, conformadas con polvos cerámicos obtenidos a través del método pechini

Tin oxide is the compound more used in the gas sensor production, mainly to reduce gases like CO and H2. Their electrical properties are strongly dependent of its surface. For this is of great importance to synthesize nanoscale tin oxide particles to use they later in the films conformation. The synthesis of SnO2-TiO2 nanoparticles by polymeric precursor method is reported in this work. The particles were characterized by DTA/TG, FT-IR, XRD and SEM. Also, the electrical response of thick films measured under oxygen and carbon monoxide atmospheres is was analyzed.

Influencia del TiO2 y Al2O3 sobre las propiedades eléctricas y microestructurales de cerámicas de SnO2 obtenidas por el método Pechini

Tin oxide has wakened up great scientific and technological interest for its potential use in varistors production and as gas sensor. In order to improve the microstructural and electrical properties in SnO varistor ceramics, the influence of differents dopants used, like TiO2 and Al2O3, is under research. The effect of TiO2 and Al2O3 on the properties of Sn-Co-Nb varistor Systems obtained by the Pechini method has been investigated in this work. Characterization of synthesized raw material was performed by X-Ray Diffraction (XRD) and Scanning Electronic Microscopy (SEM). The microstructural and electrical characterization of sintered samples show that the TiO2 favors the grain growth and the Al2O3, contributes to the decrease it, effect that is manifested in the Sn-Co-Nb varistor systems. Breakdown field increase up to 6300V/cm with increasing Al2O3 content and non-linear coefficients with α=22 were obtained.

Optical excitation of charge carriers from intra-bandgap states in Ce-doped SnO2 thin films

Optical excitation of Ce3+-doped SnO2 thin films, obtained by the sol-gel-dip-coating technique, is carried out and the effects on electrical transport are evaluated. Samples are doped with O. lat% of Ce, just above the saturation limit. The excitation is done with an intensity-controlled halogen-tungsten lamp through an interference filter, yielding an excitation wavelength of 513nm, 9 nm wide (width at half intensity peak). Irradiation at low temperature (25K) yields a conductivity increase much lower than above bandgap light. Such a behavior assures the ionization of intra-bandgap defect levels, since the filter does not allow excitation of electron-hole pairs, what would happen only in the UV range (below about 350nm). The decay of intra-bandgap excited levels in the range 250-320 K is recorded, leading to a temperature dependent behavior related to a thermally excited capture cross section for the dominating defect level. © 2008 American Institute of Physics.

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.

Effect of seed addition on SnO2-based varistors for low voltage application

The effect of seed addition on the microstructure and non-ohmic properties of the SnO2 + 1%CoO + 0.05%Nb2O5 ceramic-based system was analyzed. Two classes of seeds were prepared: 99% SnO2 + 1%CuO and 99% SnO2 + 1%CoO (mol%); both classes were added to the ceramic-based system in the amount of 1%, 5%, and 10%. The two systems containing 1% of seeds resulted in a larger grain size and a lower breakdown voltage. The addition of 1% copper seeds produces a breakdown voltage (V b) of ∼ 37 V and a leakage current (fic) of 29 μA. On the other hand, the addition of 1% cobalt seeds produced a breakdown voltage of 57 V and a leakage current of 70 μA. Both systems are of great technological interest for low voltage varistor applications, by means of appropriate strategies to reduce the leakage current. Using larger amounts of seeds was not effective since the values of breakdown voltage in both cases are close to a system without seeds. To our knowledge, there are no reports in the literature regarding the use of seeds in the SnO2 system for low voltage applications. A potential barrier model which illustrates the formation of oxygen species (O′2(ads), O′ads, and O″ads) at the expense of clusters near the interface between grains is proposed. © 2012 The American Ceramic Society.