Formation energetics and magnetism in Ca/TM doped CaZrO3: DFT investigation

Highlights: • Formation energy strongly depends on TM size. • Ti-doped system is energetically favorable. • Half-metallic ferromagnetic state is evident for V, Cr, Fe, and Co-doped systems. - Abstract: Spin-polarized density functional theory is used to investigate the formation energetics and magnetic properties of Ca/transition metal TM (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, and Cu) doped CaZrO₃ systems. A strong interdependence of formation energy and TM dopant size (ionic radii) is evident, which increases solely with the increase of dopant atomic number. Our results elucidate that Co@Zr, Cr@Zr, Fe@Zr, and V@Zr doped systems show half-metallic nature due to partial filling of d-orbitals with a reasonable charge carrier density of ∼10²¹ cm⁻³, while Ca@Zr and Cu@Zr doped systems exhibit p-type ferromagnetism because of deficiency of electrons. In contrast, Sc-dopant reveals as p-type non-magnetic due to strong hybridization. Furthermore, Ti@Zr, Mn@Zr, and Ni@Zr doped CaZrO₃ systems, depict non-magnetic behavior. Interestingly, Mn@Zr doped system contains high magnetic moment of 3μ_B and show insulating nature. The findings of present calculations yield a wide avenue for practical applications of these doped systems in spintronics.