Magnetite (Fe3O4) is of fundamental importance for the Verwey transition near TV = 125 K, below which a complex lattice distortion and electron orders occur. The Verwey transition is suppressed by chemical doping effects giving rise to well-documented first and second-order regimes, but the origin of the order change is unclear. Here, we show that slow oxidation of monodisperse Fe3O4 nanoparticles leads to an intriguing variation of the Verwey transition: an initial drop of TV to a minimum at 70 K after 75 days and a followed recovery to 95 K after 160 days. A physical model based on both doping and doping-gradient effects accounts quantitatively for this evolution between inhomogeneous to homogeneous doping regimes. This work demonstrates that slow oxidation of nanoparticles can give exquisite control and separation of homogeneous and inhomogeneous doping effects on the Verwey transition and offers opportunities for similar insights into complex electronic and magnetic phase transitions in other materials.
Most interesting phenomena of condensed matter physics originate from interactions among different degrees of freedom, making it a very intriguing yet challenging question how certain ground states emerge from only a limited number of atoms in assembly. This is especially the case for strongly correlated electron systems with overwhelming complexity. The Verwey transition of Fe3O4 is a classic example of this category, of which the origin is still elusive 80 years after the first report. Here we report, for the first time, that the Verwey transition of Fe3O4 nanoparticles exhibits size-dependent thermal hysteresis in magnetization, 57Fe NMR, and XRD measurements. The hysteresis width passes a maximum of 11 K when the size is 120 nm while dropping to only 1 K for the bulk sample. This behavior is very similar to that of magnetic coercivity and the critical sizes of the hysteresis and the magnetic single domain are identical. We interpret it as a manifestation of charge ordering and spin ordering correlation in a single domain. This work paves a new way of undertaking researches in the vibrant field of strongly correlated electron physics combined with nanoscience.
Fe nuclear magnetic resonance (NMR) of magnetite nanocrystals ranging in size from 7 nm to 7 μm is measured. The line width of the NMR spectra changes drastically around 120 K, showing microscopic evidence of the Verwey transition. In the region above the transition temperature, the line width of the spectrum increases and the spin-spin relaxation time decreases as the nanocrystal size decreases. The line-width broadening indicates the significant deformation of magnetic structure and reduction of charge order compared to bulk crystals, even when the structural distortion is unobservable. The reduction of the spin-spin relaxation time is attributed to the suppressed polaron hopping conductivity in ferromagnetic metals, which is a consequence of the enhanced electron-phonon coupling in the quantum-confinement regime. Our results show that the magnetic distortion occurs in the entire nanocrystal and does not comply with the simple model of the core-shell binary structure with a sharp boundary.
The rare-earth pyrosilicate family of compounds (RE2Si2O7) hosts a variety of polymorphs, some with honeycomb-like geometries of the rare-earth sublattices, and the magnetism has yet to be deeply explored in many of the cases. Here we report on the ground state properties of C–Er2Si2O7. C–Er2Si2O7 crystallizes in the C2/m space group and the Er3+ atoms form a distorted honeycomb lattice in the a–b plane. We have utilized specific heat, DC susceptibility, and neutron diffraction measurements to characterize C–Er2Si2O7. Our specific heat and DC susceptibility measurements show signatures of antiferromagnetic ordering at 2.3 K. Neutron powder diffraction confirms this transition temperature and the relative intensities of the magnetic Bragg peaks are consistent with a collinear Néel state in the magnetic space group C2’/m, with ordered moment of 6.61 μ
B
canted 13° away from the c-axis toward the a-axis. These results are discussed in relation to the isostructural quantum dimer magnet compound Yb2Si2O7.
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