A Ca substitution study of NaV2O4: High-pressure synthesis of the Na1?xCaxV2O4 solid solution

Ambient pressure CaV₂O₄ and high-pressure NaV₂O₄ crystallize in the CaFe₂O₄ structure type containing double chains of edge-sharing VO₆ octahedra. Recent measurements on NaV₂O₄ reveal low-dimensional metallicity and evidence of half-metallic ferromagnetism. In contrast, CaV₂O₄ is an antiferromagnetic insulator. To explore the evolution of these ground-state behaviors, we have prepared a series of Ca-doped NaV₂O₄ compounds with the formula Na_1?xCa_xV₂O₄ (x = 0–1) using high-pressure synthesis. Samples at the Na end (x = 0–0.07) show a broad antiferromagnetic transition in the 120–160 K range in accordance with earlier reports. Transport measurements show an insulator–metal transition at x ～ 0.2. Samples with higher Ca concentrations (x = 0.4–0.7) exhibit a metal–insulator transition around 150 K. The results for the Na_1?xCa_xV₂O₄ solid solution is discussed in comparison to existing studies at the Ca- and Na-rich ends.