Mechanism of Formation of the Thermoelectric Layered Cobaltate Ca3Co4O9 by Annealing of CaO-CoO Thin Films

• The layered cobaltate Ca3Co4O9 is of interest for energy-harvesting and heat-conversion applications because of its good thermoelectric properties and the fact that the raw materials Ca and Co are nontoxic, abundantly available, and inexpensive. While single-crystalline Ca3Co4O9 exhibits high Seebeck coefficient and low resistivity, its widespread use is hampered by the fact that single crystals are too small and expensive. A promising alternative approach is the growth of highly textured and/or epitaxial Ca3Co4O9 thin films with correspondingly anisotropic properties. Here, we present a two-step sputtering/annealing method for the formation of highly textured virtually phase-pure Ca3Co4O9 thin films by reactive cosputtering from Ca and Co targets followed by an annealing process at 730 °C under O2-gas flow. The thermally induced phase transformation mechanism is investigated by in situ time-resolved annealing experiments using synchrotron-based 2D X-ray diffraction (XRD) as well as ex situ annealing experiments and standard lab-based XRD. By tuning the proportion of initial CaO and CoO phases during film deposition, the method enables synthesis of Ca3Co4O9 thin films as well as CaxCoO2. With this method, we demonstrate production of epitaxial Ca3Co4O9 thin films with in-plane electrical resistivity of 6.44 mΩ cm and a Seebeck coefficient of 118 μV K−1 at 300 K.

Subject headings

NATURVETENSKAP  -- Fysik -- Den kondenserade materiens fysik (hsv//swe)

NATURAL SCIENCES  -- Physical Sciences -- Condensed Matter Physics (hsv//eng)

TEKNIK OCH TEKNOLOGIER  -- Materialteknik -- Annan materialteknik (hsv//swe)

ENGINEERING AND TECHNOLOGY  -- Materials Engineering -- Other Materials Engineering (hsv//eng)

TEKNIK OCH TEKNOLOGIER  -- Nanoteknik (hsv//swe)

ENGINEERING AND TECHNOLOGY  -- Nano-technology (hsv//eng)

Keyword

Thermoelectrics

Ca3Co4O9

thin film

sputtering

phase transformation

Publication and Content Type

ref (subject category)

art (subject category)