In situ observation of phase transitions in La2NiO4+δ bulk and thin film samples via Raman spectroscopy

La₂NiO_4+δ has attracted increasing interest in recent years, both as oxygen electrode in solid oxide fuel cells and electrolysers due to its high electrochemical activity at intermediate-to-low temperatures, and as key component of memristive devices for neuromorphic computing, owing to its variable oxygen stoichiometry. The integration of La₂NiO_4+δ into devices operating at different temperatures and oxygen partial pressures requires knowledge of the effects of hyper-stoichiometry (δ) on its crystalline structure. La₂NiO_4+δ is known to accommodate oxygen at interstitial sites allowing for large δ values, up to ∼ 0.16. In addition, the O-doping - temperature phase diagram is known to be complex, exhibiting several phase transitions with increasing δ. Herein, we use Raman spectroscopy to monitor the effects of O-doping in the phase diagram and the various structures it contains. Throughout this work, we studied this material in its usual ceramic form, as well as in the form of thin films. Results are discussed in terms of phase transitions, chemical expansion, and some of the possible consequences of the low mean grain size inherent to such thin films.