Thermoelectric Properties of Oxygen-Tuned ALD-Grown [Ca₂CoO₃]0.62[CoO₂] Thin Films

Thin films of the p -type thermoelectric misfit-layered oxide, [Ca 2 CoO 3 ] 0.62 [CoO 2 ], were prepared for the first time by means of the atomic layer deposition (ALD) technique using Ca(thd) 2, Co(thd) 2, and O 3 as precursors. As-deposited films were amorphous; however, with heat treatment in an O 2 gas flow, well-crystallized highly c -axis-oriented [Ca 2 CoO 3 ] 0.62 [CoO 2 ] films were obtained. The oxygen content of the O 2 -annealed film was further controlled through a reductive N 2 -annealing. Because the degree of reduction was dependent on the annealing temperature, the choice of N 2 -annealing temperature provided us with a tool for precise tuning of the oxygen content. With decreasing oxygen content, the lattice parameter ( c ) and the Seebeck coefficient ( S ) were found to increase. The room-temperature S values were 113 and 128 μV/K for the oxygen-richest sample and the most-reduced sample, respectively.