Effects of spin entropy and lattice strain from mixed-trivalent Fe3+/Cr3+ on the electronic, thermoelectric and optical properties of delafossite CuFe1−xCrxO2 (x = 0.25, 0.5, 0.75)

Abstract

Mixed-trivalent Fe3+/Cr3+ content CuFe1−xCrxO2 (x = 0.25, 0.5, and 0.75) compounds were synthesized to investigate the effects of spin entropy, and lattice strain on their electronic, thermoelectric and optical properties. The XPS results showed the existence of mixed Cu1+/Cu2+, Fe3+/Fe4+ and Cr2+/Cr3+ ion states in the structures. The mixed Fe3+/Cr3+ions caused a strong correlation to occur between the spin and the orbitals of the carriers in the octahedral layer of the sample, affecting the carrier degeneracy Seebeck coefficient behaviour, and the Cu2+ and Fe4+ ions caused an effect of enhancing the electric conductivity. These effects meant that CuFe0.75Cr0.25O2 had the highest electrical conductivity, an enhanced Seebeck coefficient compared to that of CuFeO2-based compounds, and the highest thermopower value. The lowest thermal conductivity was that of CuFe0.5Cr0.5O2, which was a result of the mismatched atomic radii of the mixed trivalent Fe3+(0.645 Å)/Cr3+(0.615 Å), which caused the lattice strain to occur in the structure and thus affected the point defect scattering of the phonon thermal conductivity. The lowest total thermal conductivity was that of CuFe0.5Cr0.5O2, because it had the maximum lattice strain. Overall, the effect of the mixed trivalent elements caused CuFe0.75Cr0.25O2 to have the highest value of the dimensionless figure of merit ZT, with a value that was four times that of CuFeO2-based compounds and six times that of CuCrO2-based compounds. With regard to optical properties, the lattice strain causes the indirect optical gap to increase with increasing x content, but has no effect on the direct optical gap. These results verified that the mixed-trivalent Fe3+/Cr3+ content of CuFe1−xCrxO2 (x = 0.25, 0.5, and 0.75) affected the electronic, thermoelectric and optical properties of the structure by causing spin entropy and lattice strain to occur.