Perovskite oxides are widely studied for a variety of applications, from theromoelectrics to fuel cells. Part of the attraction lies in the fact that perovskite ceramics are relatively easy to dope chemically over a wide range of compositions, resulting in various degrees of structural ordering [1]. As a consequence, the properties and functionalitiesof such materials can be readily tailored [2] . For instance in systems proposed for thermoelectric applications, the presence of superlattices,

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... domain boundaries vacancies can suppress the thermal conductivity due to increased phonon scattering [3, 4] . Understanding therefore the mechanisms behind the formation of such types of ordering in ceramic systems is crucial for their implementation in engineering applications.