N. Theodoropoulou

Wide band gap ferromagnetic semiconductors and oxides

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 ZnO) 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, Cr) as suggested by theory [see, for example, Sato and Katayama-Yoshida, Jpn. J. Appl. Phys., Part 2 39, L555 (2000)]. 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. T...

Ferromagnetism in Mn-implanted ZnO:Sn single crystals

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 segreg...

Magnetic and structural properties of Mn-implanted GaN

High doses (1015–5×1016 cm−2) of Mn+ ions were implanted into p-GaN at ∼350 °C and annealed at 700–1000 °C. At the high end of this dose range, platelet structures of GaxMn1−xN were formed. The presence of these regions correlated with ferromagnetic behavior in the samples up to ∼250 K. At low doses, the implanted led to a buried band of defects at the end of the ion range.

Indication of ferromagnetism in molecular-beam-epitaxy-derived N-type GaMnN

Growth by molecular-beam epitaxy of the dilute magnetic alloy GaMnN is reported. The GaMnN contains 7.0% Mn as determined by Auger electron spectroscopy, and is single phase as determined by x-ray diffraction and reflection high-energy electron diffraction. Both magnetic and magnetotransport data are reported. The results show the anomalous Hall effect, negative magnetoresistance, and magnetic hysteresis at 10 K, indicating that Mn is incorporating into the GaN and forming the ferromagnetic semiconductor GaMnN. At 25 K the anomalous Hall term vanishes, indicating a Curie temperature between 10 and 25 K.

Unconventional carrier-mediated ferromagnetism above room temperature in ion-implanted (Ga, Mn)P:C.

Ion implantation of Mn ions into hole-doped GaP has been used to induce ferromagnetic behavior above room temperature for optimized Mn concentrations near 3 at. %. The magnetism is suppressed when the Mn dose is increased or decreased away from the 3 at. % value, or when n-type GaP substrates are used. At low temperatures the saturated moment is on the order of 1 Bohr magneton, and the spin wave stiffness inferred from the Bloch-law T(3/2) dependence of the magnetization provides an estimate T(c)=385 K of the Curie temperature that exceeds the experimental value, T(c)=270 K. The presence of ferromagnetic clusters and hysteresis to temperatures of at least 330 K is attributed to disorder and proximity to a metal-insulating transition.

Ferromagnetism in Co- and Mn-doped ZnO

Bulk single crystals of Sn-doped ZnO were implanted with Co or Mn at doses designed to produce transition metal concentrations of 3–5 at.% in the near-surface (� 2000 A region. The implantation was performed at � 350 Ct o promote dynamic annealing of ion-induced damage. Following annealing at 700 C, temperature-dependent magnetization measurements showed ordering temperatures of � 300 K for Co- and � 250 K for Mn-implanted ZnO. Clear hysteresis loops were obtained at these temperatures. The coercive fields were 6 100 Oe for all measurement temperatures. X-ray diffraction showed no detectable second phases in the Mn-implanted material. One plausible origin for the ferromagnetism in this case is a carrier-induced mechanism. By sharp contrast, the Co-implanted material showed evidence for the presence of Co precipitates with hexagonal symmetry, which is the cause of the room temperature ferromagnetism. Our results are consistent with the stabilization of ferromagnetic states by electron doping in transition metal-doped ZnO predicted by Sato and Katayama–Yoshida [Jpn. J. Appl. Phys. 40 (2001) L334]. This work shows the excellent promise of Mn-doped ZnO for potential room temperature spintronic applications. 2003 Elsevier Ltd. All rights reserved.

Use of ion implantation to facilitate the discovery and characterization of ferromagnetic semiconductors

The discovery of epitaxially grown ferromagnetic, type III–V semiconductors (Ga,Mn)As (Tc=110 K) and (In,Mn)As (Tc=35 K) holds promise for developing semiconductor electronics that utilize the electron’s spin degree of freedom in addition to its charge. It has been theoretically predicted that some semiconducting systems could be ferromagnetic above room temperature, when optimally doped (p-GaN with 5% Mn). We report here on the use of ion implantation to incorporate magnetic ions into a variety of semiconducting substrates, thereby facilitating investigation of the nature of ferromagnetism in semiconducting systems that are difficult to grow with other methods. The magnetic ions, Mn, Fe, and Ni, were implanted into each of the epitaxially grown semiconductors GaN, GaP, and SiC to achieve volume concentrations between 1 and 5 at. %. The implanted samples were subsequently annealed at 700–1000 °C to recrystallize the samples and remove implant damage. The implanted samples were examined with both x-ray dif...

Properties of Mn-doped Cu2O semiconducting thin films grown by pulsed-laser deposition

Abstract Semiconducting oxides offer the potential for exploring and understanding spin-based functionality in a semiconducting host material. Theoretical predictions suggest that carrier-mediated ferromagnetism should be favored for p-type material. Cu2O is a p-type, direct wide bandgap oxide semiconductor that may hold interest in exploring spin behavior. In this paper, the properties of Mn-doped Cu2O are described. Activities focused on understanding Mn incorporation during thin-film synthesis, as well as magnetic characterization. The epitaxial films were grown by pulsed-laser deposition. X-ray diffraction was used to determine film crystallinity and to address the formation of secondary phases. SQUID magnetometry was employed to characterize the magnetic properties. Ferromagnetism is observed in selected Mn-doped Cu2O films, but appears to be associated with Mn3O4 secondary phases. In phase-pure Mn-doped Cu2O films, no evidence for ferromagnetism is observed.

Magnetic and structural properties of Fe, Ni, and Mn-implanted SiC

Direct implantation of Fe, Ni or Mn at doses of 3–5×1016 cm−2 into p-type 6H-SiC substrates was carried out at a sample temperature of ∼350 °C. Subsequent annealing was performed at 700–1000 °C for 5 mins. Residual damage in the form of end-of-range defects and dislocation loops in the region from the surface to a depth of ∼0.20 μm were examined by transmission electron microscopy. To the sensitivity of both x-ray diffraction and selected area diffraction pattern analysis, no secondary phases could be detected. Signatures of ferromagnetism were observed in all the highest dose samples, with apparent Curie temperatures of 50 K (Ni), 250 K (Mn), and 270 K (Fe).

Characterization of high dose Fe implantation into p-GaN

High concentrations (3–5 at. %) of Fe were incorporated into p-GaN by direct implantation at elevated substrate temperature (350 °C). Subsequent annealing at 700 °C produced apparent ferromagnetic behavior up to ∼250 K for the 3 at. % sample. Selected area diffraction patterns did not reveal the presence of any other phases in the Fe-implanted region. The direct implantation process appears promising for examining the properties of magnetic semiconductors with application to magnetotransport and magneto-optical devices.