Unusual Phase Formation in Reactively Sputter‐Deposited La—Co—O Thin‐Film Libraries. Issue 3 (1st October 2022)

• Record Type: Journal Article
• Authors: Piotrowiak, Tobias Horst; Zehl, Rico; Suhr, Ellen; Banko, Lars; Kohnen, Benedikt; Rogalla, Detlef; Ludwig, Alfred
• Is Part Of: Advanced engineering materials. Volume 25:Issue 3(2023)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-10-01
• Subjects: perovskite -- phase-formation -- reactive magnetron sputter-deposition -- single-phase; Materials -- Periodicals; 620.11
• DOI: 10.1002/adem.202201050
• Languages: English
• ISSNs: 1438-1656

Abstract

Abstract : La‐based perovskites are versatile materials that are of interest for solid oxide fuel cells and electrocatalytic water splitting. During fabrication of composition spread thin‐film libraries of La—Co‐based oxide systems, an unusual phase formation phenomenon is observed: instead of the expected continuous composition gradient, single‐phase regions with homogeneous composition form (La2 O3 or stoichiometric La‐perovskite). This phenomenon, which occurs during reactive cosputtering, is independent of the used substrate. However, a dependency on the O2 ‐portion in the process gas and the substrate temperature is observed. It can be described as a self‐organized growth, where excess transition metal cannot be incorporated into the lattices of the forming single‐phase regions, and therefore, not into the growing film. It is hypothesized that due to the high reactivity of La and the significantly low formation energies of La2 O3 and La‐perovskites, the reactive sputter deposition of La‐based oxide films, which is a physical vapor deposition process, can turn partially—regarding film growth—into a chemical vapor deposition‐like process. The described single‐phase regions form and lead to a discontinuous composition spread, with preferred growth of the thermodynamically most stable phases. This phenomenon can be leveraged for the exploration of multinary perovskite thin‐film libraries, where the B‐site atoms of La‐perovskites are systematically substituted. Abstract : For the reactive cosputter deposition of La‐based transition metal oxide systems like La—Co—O an unusual phase formation and film growth phenomenon is observed. The sputtered gradient forms extended single‐phase regions of pure La2 O3 and LaCoO3 perovskite along the compositional axis, where excess Co is neither incorporated into the stoichiometric phases nor the growing film.