We constructed the magnetic field-temperature phase diagrams of new quasi-two-dimensional isosceles triangular lattice antiferromagnets (TLAF) Ca 3 MNb 2 O 9 (M=Co, Ni) from dc and ac magnetic susceptibilities, specific heat, dielectric constant, and electric polarization measurements on single crystalline samples. Ca 3 CoNb 2 O 9 with effective spin-1/2 Co 2+ ions undergoes a two-step antiferromagnetic phase transition at T N1 = 1.3 K and T N2 = 1.5 K and enters a stripe ordered state at zero magnetic field. With increasing field, successive magnetic phase transitions, reminiscent of the up-up-down ( uud ) and the oblique phases, are observed. The dielectric constant of Ca 3 CoNb 2 O 9 shows anomalies related to the magnetic phase transitions, but clear evidence of ferroelectricity is absent. Meanwhile, Ca 3 NiNb 2 O 9 with spin-1 Ni 2+ ions also shows a two-step antiferromagnetic transition at T N1 = 3.8 K and T N2 = 4.2 K at zero field. For Ca 3 NiNb 2 O 9 , the electric polarization in the magnetic ordered phases was clearly observed from the pyroelectric current measurements, which indicates its coexistence of magnetic ordering and ferroelectricity. 
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                            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
- 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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