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

Phase evolution of radio frequency magnetron sputtered Cr-rich (Cr,Zr)2O3(Cr,Zr)_{2}O_{3} coatings studied by in situ synchrotron X-ray diffraction during annealing in air or vacuum

The phase evolution of reactive radio frequency (RF) magnetron sputtered Cr0.28Zr0.10O0.61 coatings has been studied by in situ synchrotron X-ray diffraction during annealing under air atmosphere and vacuum. The annealing in vacuum shows t-ZrO2 formation starting at ∼750–800 °C, followed by decomposition of the a-Cr2O3 structure in conjunction with bcc-Cr formation, starting at ∼950 °C. The resulting coating after annealing to 1140 °C is a mixture of t-ZrO2, m-ZrO2, and bcc-Cr. The air-annealed sample shows t-ZrO2 formation starting at ∼750 °C. The resulting coating after annealing to 975 °C is a mixture of t-ZrO2 and a-Cr2O3 (with dissolved Zr). The microstructure coarsened slightly during annealing, but the mechanical properties are maintained, with no detectable bcc-Cr formation. A larger t-ZrO2 fraction compared with a-Cr2O3 is observed in the vacuum-annealed coating compared with the air-annealed coating at 975 °C. The results indicate that the studied pseudo-binary oxide is more stable in air atmosphere than in vacuum

Phase evolution of radio frequency magnetron sputtered Cr-rich (Cr,Zr)(2)O-3 coatings studied by in situ synchrotron X-ray diffraction during annealing in air or vacuum

The phase evolution of reactive radio frequency (RF) magnetron sputtered Cr0.28Zr0.10O0.61 coatings has been studied by in situ synchrotron X-ray diffraction during annealing under air atmosphere and vacuum. The annealing in vacuum shows t-ZrO2 formation starting at similar to 750-800 degrees C, followed by decomposition of the alpha-Cr2O3 structure in conjunction with bcc-Cr formation, starting at similar to 950 degrees C. The resulting coating after annealing to 1140 degrees C is a mixture of t-ZrO2, m-ZrO2, and bcc-Cr. The air-annealed sample shows t-ZrO2 formation starting at similar to 750 degrees C. The resulting coating after annealing to 975 degrees C is a mixture of t-ZrO2 and alpha-Cr2O3 (with dissolved Zr). The microstructure coarsened slightly during annealing, but the mechanical properties are maintained, with no detectable bcc-Cr formation. A larger t-ZrO2 fraction compared with alpha-Cr2O3 is observed in the vacuum-annealed coating compared with the air-annealed coating at 975 degrees C. The results indicate that the studied pseudo-binary oxide is more stable in air atmosphere than in vacuum.Funding Agencies|Swedish Research Council (VR)Swedish Research Council [621-20124368, 330-2014-6336]; Knut and Alice Wallenberg FoundationKnut &amp; Alice Wallenberg Foundation; Swedish Government Strategic Research Area in Materials Science on Functional Materials at Linkoping University (Faculty Grant SFO-Mat-LiU) [2009 00971]; Marie Sklodowska Curie Actions, Cofund, Project INCA [600398]; Swedish Foundation for Strategic Research (SSF) through the Future Research Leaders 6 program; Swedish Research Council via the Rontgen Angstrom Cluster (RAC) Frame Program [2011-6505]; German Federal Ministry of Education and Research (BMBF)Federal Ministry of Education &amp; Research (BMBF) [05K12CG1]</p