This report discusses important microstructural features of SnO2.MnO-based polycrystalline ceramics. The influence of the sintering time and the concentration of donor Nb2O5 on the microstructure of these ceramics are investigated, and the correlation between the microstructural features and nonohmic behavior are also discussed. High resolution analytical electron microscopy was used for a detailed characterization of the microstructure and grain boundary chemistry of the compositions, revealing that SnO2-MnO dense ceramics consist of two phases, SnO2 grains and Mn2SnO4, precipitated mainly at triple grain points. In addition, two types of SnO2-SnO2 grain boundary were identified: type I, Mn-rich and thin, and type II, Mn-poor and thick. Changes in Mn concentrations at the grain boundaries are ascribed to both grain misorientation and Mn diffusivity along the grain boundary. The identification of two kinds of junctions in SnO2-MnO has significant implications in the material’s nonohmic behavior, as will be discussed in detail here and in Part II, and is important in understanding the sintering mechanism and microstructural formation of SnO2 ceramics.

An intense and broad visible photoluminescence ͑PL͒ band was observed at room temperature in structurally disordered PbWO 4 thin films. The scheelite lead tungstate ͑PbWO 4 ͒ films prepared by the polymeric precursor method and annealed at different temperatures were structurally characterized by means of x-ray diffraction and atomic force microscopy analysis. Quantum-mechanical calculations showed that the local disorder of the network modifier ͑Pb͒ has a very important role in the charge transfer involved in the green PL emission. The experimental and theoretical results are in good agreement, both indicating that the generation of the intense visible PL band is related to simultaneous structural order and disorder in the scheelite PbWO 4 lattice.

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The SrWO 4 (SWO) powders were synthesized by the polymeric precursor method and annealed at different temperatures. The SWO structure was obtained by X-ray diffraction and the corresponding photoluminescence (PL) spectra was measured. The PL results reveal that the structural order-disorder degree in the SWO lattice influences in the PL emission intensity. Only the structurally order-disordered samples present broad and intense PL band in the visible range. To understand the origin of this phenomenon, we performed quantum-mechanical calculations with crystalline and order-disordered SWO periodic models. Their electronic structures were analyzed in terms of band structure. The appearance of localized levels in the band gap of the order-disordered structure was evidenced and is a favorable condition for the intense PL to occur.