Size-dependent magnetism in nanocrystals of spin-chain α-CoV2O6

Magnetization and high-field ESR measurements have been performed to study the magnetism of nanocrystals of α-CoV2O6, an Ising spin-chain system without triangular lattice but presenting interesting 1/3 magnetization step. The results demonstrated the antiferromagnetic (AFM) enhancement and gradual suppression of the 1/3 magnetization step in nanoparticle samples. Within the framework of core–shell model consisting of the AFM core spins and the uncompensated/disordered shell spins, the AFM enhancement below TN=13K is a result of enhanced shell disorder with weak ferromagnetism. This AFM enhancement, along with the suppression of saturation magnetization, results in the suppression of 1/3 magnetization step. Furthermore, the paramagnetism of the shell was confirmed by our high-field ESR measurements. The time-dependent magnetization suggests the presence of spin-glass-like freezing. This is expected for nanoparticles with surface shell disorder with ferromagnetic correlations, but is not expected for bulk material of α-CoV2O6 without spin frustration. These findings demonstrate that size tuning is an effective parameter for controlling the ground state of α-CoV2O6.