Ferromagnetism in defect-ridden oxides and related materials

The existence of high-temperature ferromagnetism in thin films and nanoparticles of oxides containing small quantities of magnetic dopants remains controversial. Some regard these materials as dilute magnetic semiconductors, while others think they are ferromagnetic only because the magnetic dopants form secondary ferromagnetic impurity phases such as cobalt metal or magnetite. There are also reports in d0 systems and other defective oxides that contain no magnetic ions. Here, we investigate TiO2 (rutile) containing 1 - 5% of iron cations and find that the room-temperature ferromagnetism of films prepared by pulsed-laser deposition is not due to magnetic ordering of the iron. The films are neither dilute magnetic semiconductors nor hosts to an iron-based ferromagnetic impurity phase. A new model is developed for defect-related ferromagnetism which involves a spin-split defect band populated by charge transfer from a proximate charge reservoir in the present case a mixture Fe2+ and Fe3+ ions in the oxide lattice. The phase diagram for the model shows how inhomogeneous Stoner ferromagnetism depends on the total number of electrons Ntot, the Stoner exchange integral I and the defect bandwidth W; the band occupancy is governed by the d-d Coulomb interaction U. There are regions of ferromagnetic metal, half-metal and insulator as well as nonmagnetic metal and insulator. A characteristic feature of the high-temperature Stoner magnetism is an an anhysteretic magnetization curve which is practically temperature independent below room temperature. This is related to a wandering ferromagnetic axis which is determined by local dipole fields. The magnetization is limited by the defect concentration, not by the 3d doping. Only 1-2 % of the volume of the films is magnetically ordered.Comment: 22 pages, 6 figure

Charge dynamics in the half-metallic ferromagnet CrO\u3csub\u3e2\u3c/sub\u3e

Infrared spectroscopy is used to investigate the electronic structure and charge carrier relaxation in crystalline films of CrO2 which is the simplest of all half-metallic ferromagnets. Chromium dioxide is a bad metal at room temperature but it has a remarkably low residual resistivity (\u3c5 \u3eμΩ cm) despite the small spectral weight associated with free carrier absorption. The infrared measurements show that low residual resistivity is due to the collapse of the scattering rate at ω\u3c2000 \u3ecm-1. The blocking of the relaxation channels at low v and T can be attributed to the unique electronic structure of a half-metallic ferromagnet. In contrast to other ferromagnetic oxides, the intraband spectral weight is constant below the Curie temperature

Magnetism and half-metallicity at the O surfaces of ceramic oxides

The occurence of spin-polarization at ZrO$_{2}$, Al$_{2}$O$_{3}$ and MgO surfaces is proved by means of \textit{ab-initio} calculations within the density functional theory. Large spin moments, as high as 1.56 $\mu_B$, develop at O-ended polar terminations, transforming the non-magnetic insulator into a half-metal. The magnetic moments mainly reside in the surface oxygen atoms and their origin is related to the existence of $2p$ holes of well-defined spin polarization at the valence band of the ionic oxide. The direct relation between magnetization and local loss of donor charge makes possible to extend the magnetization mechanism beyond surface properties

Magnetic field screening and mirroring in graphene

The orbital magnetism in spatially varying magnetic fields is studied in monolayer graphene within the effective mass approximation. We find that, unlike the conventional two-dimensional electron system, graphene with small Fermi wave number k_F works as a magnetic shield where the field produced by a magnetic object placed above graphene is always screened by a constant factor on the other side of graphene. The object is repelled by a diamagnetic force from the graphene, as if there exists its mirror image with a reduced amplitude on the other side of graphene. The magnitude of the force is much greater than that of conventional two-dimensional system. The effect disappears with the increase of k_F.Comment: 5 pages, 3 figure

Structure, site-specific magnetism and magneto-transport properties of epitaxial D022_{22} Mn2_2Fex_xGa thin films

Ferrimagnetic Mn$_2$Fe$_x$Ga $(0.26 \leq x \leq 1.12)$ thin films have been characterised by X-ray diffraction, SQUID magnetometry, X-ray absorption spectroscopy, X-ray magnetic circular dichroism and M\"{o}ssbauer spectroscopy with the aim of determining the structure and site-specific magnetism of this tetragonal, D0$_{22}$-structure Heusler compound. High-quality epitaxial films with low RMS surface roughness ($\sim 0.6$ nm) are grown by magnetron co-sputtering. The tetragonal distortion induces strong perpendicular magnetic anisotropy along the $c$-axis with a typical coercive field $\mu_0 H\sim 0.8$ T and an anisotropy field ranging from $6$ to $8$ T. Upon increasing the Fe content $x$, substantial uniaxial anisotropy, $K_\mathrm{u} \geq 1.0$ MJ/m$^3$ can be maintained over the full $x$ range, while the magnetisation of the compound is reduced from $400$ to $280$ kA/m. The total magnetisation is almost entirely given by the sum of the spin moments originating from the ferrimagnetic Mn and Fe sublattices, with the latter being coupled ferromagnetically to one of the former. The orbital magnetic moments are practically quenched, and have negligible contributions to the magnetisation. The films with $x=0.73$ exhibit a high anomalous Hall angle of $2.5$ % and a high Fermi-level spin polarisation, above $51$ %, as measured by point contact Andreev reflection. The Fe-substituted Mn$_2$Ga films are highly tunable with a unique combination of high anisotropy, low magnetisation, appreciable spin polarisation and low surface roughness, making them very strong candidates for thermally-stable spin-transfer-torque switching nanomagnets with lateral dimensions down to $10$ nm.Comment: 11 pages, 11 figure

Growth, transport, and magnetic properties of Pr0.67Ca0.33MnO3 thin films

We have grown Pr0.67Ca0.33MnO3 thin films on LaAlO3 using pulsed laser deposition. Below 50 K, a field induced insulator-metal transition results in changes in resistivity of at least 6 orders of magnitude. The field induced conducting state is metastable at low temperature. The temperature dependence of the resistivity exhibits considerable hysteresis in a field of 40 kOe but becomes reversible in a field of 80 kOe

Magnetization and Anisotropy of Cobalt Ferrite Thin Films

The magnetization of thin films of cobalt ferrite frequently falls far below the bulk value of 455 kAm-1, which corresponds to an inverse cation distribution in the spinel structure with a significant orbital moment of about 0.6 muB that is associated with the octahedrally-coordinated Co2+ ions. The orbital moment is responsible for the magnetostriction and magnetocrystalline anisotropy, and its sensitivity to imposed strain. We have systematically investigated the structure and magnetism of films produced by pulsed-laser deposition on different substrates (TiO2, MgO, MgAl2O4, SrTiO3, LSAT, LaAlO3) and as a function of temperature (500-700 C) and oxygen pressure (10-4 - 10 Pa). Magnetization at room-temperature ranges from 60 to 440 kAm-1, and uniaxial substrate-induced anisotropy ranges from +220 kJm-3 for films on deposited on MgO (100) to -2100 kJm-3 for films deposited on MgAl2O4 (100), where the room-temperature anisotropy field reaches 14 T. No rearrangement of high-spin Fe3+ and Co2+ cations on tetrahedral and octahedral sites can reduce the magnetization below the bulk value, but a switch from Fe3+ and Co2+ to Fe2+ and low-spin Co3+ on octahedral sites will reduce the low-temperature magnetization to 120 kAm-1, and a consequent reduction of Curie temperature can bring the room-temperature value to near zero. Possible reasons for the appearance of low-spin cobalt in the thin films are discussed. Keywords; Cobalt ferrite, thin films, pulsed-laser deposition, low-spin Co3+, strain engineering of magnetization