This review article first presents a summary of current understanding of the magnetic properties and intrinsic ferromagnetism of transition-metal (TM)-doped ZnO films, which are typical diluted magnetic oxides used in spintronics. The local structure and magnetic behavior of TM-doped ZnO are strongly sensitive to the preparation parameters. In the second part, we discuss in detail the effects of doping elements and concentrations, oxygen partial pressure, substrate and its orientation and temperature, deposition rate, post-annealing temperature and co-doping on the local structure and subsequent ferromagnetic ordering of TM-doped ZnO. It is unambiguously demonstrated that room-temperature ferromagnetism is strongly correlated with structural defects, and the carriers involved in carrier-mediated exchange are by-products of defects created in ZnO. The third part focuses on recent progress in TM-doped ZnO-based spintronics, such as magnetic tunnel junctions and spin field-effect transistors, which provide a route for spin injection from TM-doped ZnO to ZnO. Thus, TM-doped ZnO materials are useful spin sources for spintronics.

Ferromagnetism and possible application in spintronics of transition-metal-doped ZnO films

Dilute magnetic oxides are transparent, wide-bandgap materials that behave ferromagnetically when doped with a few percent of a magnetic 3d cation. The magnetism, which appears well below the cation percolation threshold, cannot be understood in terms of the conventional theory of magnetism in insulators; nor can a carrier-mediated ferromagnetic exchange mechanism account for the magnitude of the Curie temperatures, which are well in excess of 400 K. The phenomenon is observed in thin films and nanocrystals, but not in well-crystallized bulk material. Experimental artefacts and segregation of secondary ferromagnetic phases can explain some observations, but the existence of a novel type of magnetism related to defects other than the magnetic dopants is a likely inference from the data.

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Dilute magnetic oxides

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 of 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 non-magnetic metal and insulator. A characteristic feature of the high-temperature Stoner magnetism is 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.

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Ferromagnetism in defect-ridden oxides and related materials

A new model is proposed for ferromagnetism associated with defects in the bulk or at the surface of nanoparticles. The basic idea is that a narrow, structured local density of states Ns(E) is associated with the defects, but the Fermi level (which may lie above or below a mobility edge) will not normally coincide with a peak in Ns(E). However, if there is a local charge reservoir, such as a dopant cation coexisting in two different charge states or a charge-transfer complex at the surface, then it may be possible for electron transfer to raise the Fermi level to a peak in the local density of states, leading to Stoner splitting of Ns(E). Spontaneous Stoner ferromagnetism can arise in percolating defect-rich regions, such as the nanoparticle surface. The charge-transfer ferromagnetism model may be applicable to a wide range of nanoparticles and thin films of dilute magnetic oxides have previously been regarded as dilute magnetic semiconductors.

https://iopscience.iop.org/article/10.1088/0022-3727/41/13/134012/pdf

Charge-transfer ferromagnetism in oxide nanoparticles

The present review takes a semiconductor physics perspective to summarize the state-of-the art of In2O3 in relation to applications. After discussing conventional and novel applications, the crystal structure, synthesis of single-crystalline material, band-structure and optical transparency are briefly introduced before focussing on the charge carrier transport properties. The issues of unintentional n-type conductivity and its likely causes, the surface electron accumulation, and the lack of p-type conductivity will be presented. Intentional doping will be demonstrated to control the electron concentration and resistivity over a wide range, but is also subject to compensation. The control of the surface accumulation in relation to Schottky and ohmic contacts will be demonstrated. In the context of scattering mechanisms, the electron mobility and its limits will be discussed. Finally, the Seebeck coefficient and its significance will be shown, and ferromagnetic doping of In2O3 will be critically discussed. With this overview most if not all ingredients for the use of In2O3 as semiconductor material in novel or improved conventional devices will be given.

http://iopscience.iop.org/article/10.1088/0268-1242/30/2/024001/pdf

Indium oxide—a transparent, wide-band gap semiconductor for (opto)electronic applications

The search for an ideal magnetic semiconductor with tunable ferromagnetic behaviour over a wide range of doping or by electrical gating is being actively pursued as a major step towards realizing spin electronics. A magnetic semiconductor having a high Curie temperature, capable of independently controlled carrier density and magnetic doping, is crucial for developing spin-based multifunctional devices. Cr-doped In2O3 is such a unique system, where the electrical and magnetic behaviour—from ferromagnetic metal-like to ferromagnetic semiconducting to paramagnetic insulator—can be controllably tuned by the defect concentration. An explicit dependence of magnetic interaction leading to ferromagnetism on the carrier density is shown. A carrier-density-dependent high Curie temperature of 850–930 K has been measured, in addition to the observation of clear magnetic domain structures in these films. Being optically transparent with the above optimal properties, Cr-doped In2O3 emerges as a viable candidate for the development of spin electronics.

S. Layne

Papers

Carrier-controlled ferromagnetism in transparent oxide semiconductors