We are reporting the effect of thickness on the Seebeck coefficient, electrical conductivity and power factor of Ca3Co4O9thin films grown on single-crystal Sapphire (0001) substrate. Pulsed laser deposition (PLD) technique was employed to deposit Ca3Co4O9films with precisely controlled thickness values ranging from 15 to 75 nm. Structural characterization performed by scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed that the growth of Ca3Co4O9on Sapphire (0001) follows the island growth-mode. It was observed that in-plane grain sizes decrease from 126 to 31 nm as the thickness of the films decreases from 75 to 15 nm. The thermoelectric power measurements showed an overall increase in the value of the Seebeck coefficient as the films’ thickness decreased. The above increase in the Seebeck coefficient was accompanied with a simultaneous decrease in the electrical conductivity of the thinner films due to enhanced scattering of the charge carriers at the grain boundaries. Because of the competing mechanisms of the thickness dependence of Seebeck coefficient and electrical conductivity, the power factor of the films showed a non-monotonous functional dependence on thickness. The films with the intermediate thickness (60 nm) showed the highest power factor (~ 0.27 mW/m-K2at 720 K).
Engineering thermoelectric and mechanical properties by nanoporosity in calcium cobaltate films from reactions of Ca(OH) 2 /Co 3 O 4 multilayers
Controlling nanoporosity to favorably alter multiple properties in layered crystalline inorganic thin films is a challenge. Here, we demonstrate that the thermoelectric and mechanical properties of Ca 3 Co 4 O 9 films can be engineered through nanoporosity control by annealing multiple Ca(OH) 2 /Co 3 O 4 reactant bilayers with characteristic bilayer thicknesses (b t ). Our results show that doubling b t , e.g. , from 12 to 26 nm, more than triples the average pore size from ∼120 nm to ∼400 nm and increases the pore fraction from 3% to 17.1%. The higher porosity film exhibits not only a 50% higher electrical conductivity of σ ∼ 90 S cm −1 and a high Seebeck coefficient of α ∼ 135 μV K −1 , but also a thermal conductivity as low as κ ∼ 0.87 W m −1 K −1 . The nanoporous Ca 3 Co 4 O 9 films exhibit greater mechanical compliance and resilience to bending than the bulk. These results indicate that annealing reactant multilayers with controlled thicknesses is an attractive way to engineer nanoporosity and realize mechanically flexible oxide-based thermoelectric materials.
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- Award ID(s):
- 2135725
- NSF-PAR ID:
- 10357436
- Date Published:
- Journal Name:
- Nanoscale Advances
- Volume:
- 4
- Issue:
- 16
- ISSN:
- 2516-0230
- Page Range / eLocation ID:
- 3353 to 3361
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Thermoelectric materials can convert heat into electricity. They are used to generate electricity when other power sources are not available or to increase energy efficiency by recycling waste heat. The Yb 21 Mn 4 Sb 18 phase was previously shown to have good thermoelectric performance due to its large Seebeck coefficient (∼290 μV K −1 ) and low thermal conductivity (0.4 W m −1 K −1 ). These characteristics stem respectively from the unique [Mn 4 Sb 10 ] 22− subunit and the large unit cell/site disorder inherent in this phase. The solid solutions, Yb 21 Mn 4− x Cd x Sb 18 ( x = 0, 0.5, 1.0, 1.5) and Yb 21− y Ca y Mn 4 Sb 18 ( y = 3, 6, 9, 10.5) have been prepared, their structures characterized and thermoelectric properties from room temperature to 800 K measured. A detailed look into the structural disorder for the Cd and Ca solid solutions was performed using synchrotron powder X-ray diffraction and pair distribution function methods and shows that these are highly disordered structures. The substitution of Cd gives rise to more metallic behavior whereas Ca substitution results in high resistivity. As both Cd and Ca are isoelectronic substitutions, the changes in properties are attributed to changes in the electronic structure. Both solid solutions show that the thermal conductivities remain extremely low (∼0.4 W m −1 K −1 ) and that the Seebeck coefficients remain high (>200 μV K −1 ). The temperature dependence of the carrier mobility with increased Ca substitution, changing from approximately T −1 to T −0.5 , suggests that another scattering mechanism is being introduced. As the bonding changes from polar covalent with Yb to ionic for Ca, polar optical phonon scattering becomes the dominant mechanism. Experimental studies of the Cd solid solutions result in a max zT of ∼1 at 800 K and, more importantly for application purposes, a ZT avg ∼ 0.6 from 300 K to 800 K.more » « less
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2NA00278G
