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Growth Mechanism, Microstructure, and Surface Modification of Nanostructured CeO 2 Films by Chemical Solution Deposition
Author(s) -
Cavallaro A.,
Sandiumenge F.,
Gàzquez J.,
Puig T.,
Obradors X.,
Arbiol J.,
Freyhardt H. C.
Publication year - 2006
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.200500206
Subject(s) - materials science , microstructure , x ray photoelectron spectroscopy , nucleation , grain boundary , crystallization , epitaxy , grain growth , chemical engineering , annealing (glass) , abnormal grain growth , transmission electron microscopy , crystallography , analytical chemistry (journal) , composite material , nanotechnology , layer (electronics) , engineering , chemistry , organic chemistry , chromatography
Abstract The evolution from a partially oriented granular microstructure to a dense epitaxial one in CeO 2 films deposited from chemical solutions on Y 2 O 3 ‐stabilized cubic ZrO 2 (YSZ) has been investigated using cross‐section transmission electron microscopy (XTEM), electron energy‐loss spectroscopy (EELS), X‐ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), X‐ray diffraction (XRD), and X‐ray reflectometry (XRR). In crystallization from chemical solutions, undercoolings are typically high enough to promote homogeneous and heterogeneous nucleation with equal probability. The desired texture is then transmitted from heterogeneously nucleated epitaxial grains throughout the volume of the film upon sintering. Crystallization of CeO 2 under the reducing atmospheric conditions of Ar/5 % H 2 results in a nanometric granular microstructure with a high concentration of C impurities decorating grain boundaries and interstitial cavities, which unexpectedly prevails after high‐temperature annealing. Post‐processing in oxidizing conditions removes C impurities and promotes grain growth resulting in a fully epitaxial film, as well as stabilizing the otherwise energetically prohibitive polar (001) planes. Misfit stresses in the post‐processed epitaxial films are completely relieved by interfacial dislocations with b = ( a /2) < 110 > and b = ( a /2) < 011 > Burgers vectors. A mechanism that considers impurity‐induced grain‐boundary blocking and the stabilization of (001) planes via surface oxidation is proposed. Processing conditions to obtain high‐quality CeO 2 buffer layers can be adapted to YBa 2 Cu 3 O 7 ‐coated conductors.