Recent advances in the theory and experimental realization of ferromagnetic semiconductors give hope that a new generation of microelectronic devices based on the spin degree of freedom of the electron can be developed. This review focuses primarily on promising candidate materials ͑such as GaN, GaP and ZnO͒ in which there is already a technology base and a fairly good understanding of the basic electrical and optical properties. The introduction of Mn into these and other materials under the right conditions is found to produce ferromagnetism near or above room temperature.There are a number of other potential dopant ions that could be employed ͑such as Fe, Ni, Co, Cr͒ as suggested by theory ͓see, for example, Sato and Katayama-Yoshida, Jpn. J. Appl. Phys., Part 2 39, L555 ͑2000͔͒. Growth of these ferromagnetic materials by thin film techniques, such as molecular beam epitaxy or pulsed laser deposition, provides excellent control of the dopant concentration and the ability to grow single-phase layers. The mechanism for the observed magnetic behavior is complex and appears to depend on a number of factors, including Mn-Mn spacing, and carrier density and type. For example, in a simple Ruderman-Kittel-Kasuya-Yosida carrier-mediated exchange mechanism, the free-carrier/Mn ion interaction can be either ferromagnetic or antiferromagnetic depending on the separation of the Mn ions. Potential applications for ferromagnetic semiconductors and oxides include electrically controlled magnetic sensors and actuators, high-density ultralow-power memory and logic, spin-polarized light emitters for optical encoding, advanced optical switches and modulators and devices with integrated magnetic, electronic and optical functionality.

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Phase competition underlies many remarkable and technologically important phenomena in transition metal oxides. Vanadium dioxide (VO2) exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. Ongoing attempts to explain this coupled structural and electronic transition begin with two alternative starting points: a Peierls MIT driven by instabilities in electron-lattice dynamics and a Mott MIT where strong electron-electron correlations drive charge localization. A key missing piece of the VO2 puzzle is the role of lattice vibrations. Moreover, a comprehensive thermodynamic treatment must integrate both entropic and energetic aspects of the transition. Here we report that the entropy driving the MIT in VO2 is dominated by strongly anharmonic phonons rather than electronic contributions, and provide a direct determination of phonon dispersions. Our ab initio calculations identify softer bonding in the tetragonal phase, relative to the monoclinic phase, as the origin of the large vibrational entropy stabilizing the metallic rutile phase. They further reveal how a balance between higher entropy in the metal and orbital-driven lower energy in the insulator fully describes the thermodynamic forces controlling the MIT. Our study illustrates the critical role of anharmonic lattice dynamics in metal oxide phase competition, and provides guidance for the predictive design of new materials.

We have investigated the magnetic properties of Mn-implanted n-type ZnO single crystals that are codoped with Sn. Theory predicts that room-temperature carrier-mediated ferromagnetism should be possible in manganese-doped p-type ZnO, although Mn-doped n-type ZnO should not be ferromagnetic. While previous efforts report only low-temperature ferromagnetism in Mn-doped ZnO that is n type via shallow donors, we find evidence for ferromagnetism with a Curie temperature of ∼250 K in ZnO that is codoped with Mn and Sn. As a 4+ valence cation, Sn should behave as a doubly ionized donor, thus introducing states deep in the gap. Hysteresis is clearly observed in magnetization versus field curves. Differences in zero-field-cooled and field-cooled magnetization persists up to ∼250 K for Sn-doped ZnO crystals implanted with 3 at. % Mn. Increasing the Mn concentration to 5 at. % significantly reduces the magnetic hysteresis. This latter observation is inconsistent with the origin for ferromagnetism being due to segregated secondary phases, and strongly suggests that a near-room-temperature dilute magnetic semiconducting oxide has been realized. Based on these results, ZnO doped with Mn and Sn may prove promising as a ferromagnetic semiconductor for spintronics.