Magnetic phase separation and unusual scenario of its temperature evolution in porous carbon-based nanomaterials doped with Au and Co

摘要

Two porous glassy carbon-based samples doped with Au and Co were investigated. The magnetization study as well as measurements of the nonlinear longitudinal response to a weak ac field (NLR) and electron magnetic resonance give evidences for a presence of magnetic nanoparticles (MNPs) embedded in paramagnetic/ferromagnetic matrix respectively, both samples being in magnetically phase-separated state at temperatures above 300 K. Matrix, forming by paramagnetic centers located in matrix outside the MNPs, reveals exchange interactions providing its ferromagnetic (FM) ordering below T_C ≈ 210 K in Au-doped sample and well above 350 K in Co-doped one. For the former, NLR data suggest a percolation character of the matrix long-range FM order, which is mainly caused by a porous amorphous sample structure. Temperature dependence of the magnetization in the Au-doped sample evidences presence of antiferromagnetic (AF) interactions of MNPs with surrounding matrix centers. At magnetic ordering below T_C these interactions promote origination of "domains" involving matrix fragment and surrounding MNPs with near opposite orientation of their moments that decreases the magnetostatic energy. On further cooling, the domains exhibit AF ordering below 7_(cr) ~ 140 K < T_C, resulting in formation of a peculiar "ferrimagnet". The porous amorphous structure leads to absence of translational and other symmetry features through the samples that allows canted ordering of magnetic moments in domains and in whole sample providing "cantedferrimagnetism". At low temperatures T_(tr) ~ 3 K, "order-oder" transition, evidencing the non-Heisenberg character of this magnetic material, occurs from ordering like "canted ferrimagnet" to FM alignment, which is stimulated by external magnetic field. The data for Co-doped sample imply the similar evolution of magnetic state but at higher temperatures above 350 K. This state exhibits more homogeneous arrangement of the FM nanoparticles and the FM matrix. Order-order transition occurs in it at higher T_(tr) ~ 10-15 K as well and followed by formation of long-range FM ordering found earlier by neutron diffraction. Doping of carbon-based nanomaterials by magnetic metals provides advantages for their possible practical applications as Co-doped sample with higher T_C (>350 K) and larger remanent magnetization evidences.