Nucleation of nanoparticles using
the exsolution phenomenon is
a promising pathway to design durable and active materials for catalysis
and renewable energy. Here, we focus on the impact of surface orientation
of the host lattice on the nucleation dynamics to resolve questions
with regards to “preferential nucleation sites”. For
this, we carried out a systematic model study on three differently
oriented perovskite thin films. Remarkably, in contrast to the previous
bulk powder-based study suggesting that the (110)-surface is a preferred
plane for exsolution, we identify that other planes such as (001)-
and (111)-facets also reveal vigorous exsolution. Moreover, particle
size and surface coverage vary significantly depending on the surface
orientation. Exsolution of (111)-oriented film produces the largest
number of particles, the smallest particle size, the deepest embedment,
and the smallest and most uniform interparticle distance among the
oriented films. Based on classic nucleation theory, we elucidate that
the differences in interfacial energies as a function of substrate
orientation play a crucial role in controlling the distinct morphology
and nucleation behavior of exsolved nanoparticles. Our finding suggests
new design principles for tunable solid-state catalyst or nanoscale
metal decoration.
This article is protected by copyright. All rights reserved. track the frequency of the oxygen stretching mode around Fe 4+ , as it decreases during reduction as the material expands and increases during re-oxidation as the material shrinks. This methodology of oxygen pumping and in situ Raman of oxide films enables future in operando measurements even for small material volumes, as typical for applications of films as electrodes or electrolytes utilized in electrochemical energy conversion or memory devices.
Thin film nonstoichiometric oxides enable many high-temperature applications including solid oxide fuel cells, actuators, and catalysis. Large concentrations of point defects (particularly, oxygen vacancies) enable fast ionic conductivity or gas exchange kinetics in these materials but also manifest as coupling between lattice volume and chemical composition. This chemical expansion may be either detrimental or useful, especially in thin film devices that may exhibit enhanced performance through strain engineering or decreased operating temperatures. However, thin film nonstoichiometric oxides can differ from bulk counterparts in terms of operando defect concentrations, transport properties, and mechanical properties. Here, we present an in situ investigation of atomic-scale chemical expansion in PrCeO (PCO), a mixed ionic-electronic conducting oxide relevant to electrochemical energy conversion and high-temperature actuation. Through a combination of electron energy loss spectroscopy and transmission electron microscopy with in situ heating, we characterized chemical strains and changes in oxidation state in cross sections of PCO films grown on yttria-stabilized zirconia (YSZ) at temperatures reaching 650 °C. We quantified, both statically and dynamically, the nanoscale chemical expansion induced by changes in PCO redox state as a function of position and direction relative to the film-substrate interface. Additionally, we observed dislocations at the film-substrate interface, as well as reduced cation localization to threading defects within PCO films. These results illustrate several key aspects of atomic-scale structure and mechanical deformation in nonstoichiometric oxide films that clarify distinctions between films and bulk counterparts and that hold several implications for operando chemical expansion or "breathing" of such oxide films.
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