Layered cobalt oxides based on the hexagonal CoO2 layer, e.g., NaxCoO2 and [CoCa3O3]0.62CoO2 (or “Ca3Co4O9”), are promising thermoelectric materials. Here, the authors investigate the atomic layer deposition (ALD) of these materials in a thin-film form; this is not trivial, in particular, for the former compound, as both Na and Co are little challenged as components of ALD thin films. The authors employ diketonate precursors for all the metal constituents and ozone as the source of oxygen. In both cases, a postdeposition heat-treatment in O2 is applied to get crystalline coatings; the processes are found amazingly robust in terms of metal precursor pulsing ratios. A striking difference between the two processes is the resultant morphology: while the Ca3Co4O9 films grow highly homogeneous and smooth, the NaxCoO2 coatings exhibit a rather unique reproducible 10–20 μm scale channel-like island structure for all x values investigated. Finally, the authors characterized their ALD Ca3Co4O9 films for their chemical, structural, and physical property details not previously reported.

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