On the room-temperature ferromagnetism in (ZnO)0.98(MnO2)0.02

Room-temperature ferromagnetism (RTFM) is investigated in the polycrystalline bulk (ZnO)_0.98(MnO₂)_0.02 samples prepared by a modified solid-state sintering route. Successive sintering of a sample was carried out in air at different temperatures in the range of 400-1000 °C. The study of magnetization and phase-investigation in the sample was carried out after each sintering step. The progressive suppression of impurities and the consequent reduction in RTFM is clearly observed in the samples with increase in the sintering temperature up to 800 °C. The subsequent successive sintering of the (ZnO)_0.98(MnO₂)_0.02 sample up to 1000 °C yields fully paramagnetic sample exhibiting wurtzite structure. The studies support the conjecture (Kundaliya et al., Nat. Mater. 3 (2004) 709 [18]) that RTFM in this system has an origin related to a randomly distributed impurity phase produced by local dissolution of ZnO and MnO₂.     

Ferromagnetism in carbon-doped ZnO films from first-principle study

First-principle calculations based on density functional theory have been performed on the nonmagnetic 2p light element C-doped ZnO thin films. The total energies and magnetism of the system are calculated with a ten-layer slab along () direction. The results show that the C-doped ZnO thin films are ferromagnetic. A single C is preferable to occupy the subsurface site. As the concentration of C atoms increases, the ferromagnetic coupling among the dopants is more favorable, and they tend to form a cluster around the Zn atom at the film surface. The ferromagnetism is predicted to be mainly from a p-d exchange-like p-p coupling interaction and a p-d exchange hybridization. The p-p coupling interaction is the dominative mechanism.     

Magnetic properties of doped ZnO prepared by different synthetic routes

We have studied the magnetic properties of Zn_0.96M_0.04O (M=Mn, Fe, Co) compounds prepared using several routes. The low temperature ceramic synthesis gave multiphasic samples and show ferromagnetic behavior. Single phases can be obtained by heating at higher temperatures (∼900–1100 °C). The use of very low oxygen pressure also favours the preparation of single-phases. We were also successful in preparing single-phase samples at very low temperature (∼400 °C) by using a sol-gel method. All of the samples without noticeable secondary phases in the X-ray patterns behave as conventional paramagnets. This is true even for the samples with very low grain size. Samples exhibiting secondary phases reveal spontaneous magnetization even at room temperature in some cases. Our results strongly support that ferromagnetism at room temperature is always due to the presence of secondary phases and not to the doping of ZnO.     

Ferromagnetism in ZnO doped with Co by ion implantation

The importance of doping ZnO with magnetic ions is associated with the fact that this oxide is a good candidate for the formation of a magnetic-diluted semiconductor. Most of the studies reported in Co-doped ZnO were carried out in thin films, but the understanding of the modification of the magnetic behaviour due to doping demands the study of single-crystalline samples. In this work, ZnO single crystals were doped at room temperature with Co by ion implantation with fluences ranging between 2×10¹⁶ and 1×10¹⁷ ions cm⁻² and implantation energy of 100 keV. As implanted samples show a superparamagnetic behaviour attributed to the formation of Co clusters, room temperature ferromagnetism is attained after annealing at 800 °C, but no magnetoresistance was detected in the temperature range from 10 to 300 K.     

Ab initio calculation and analysis of the properties of digital magnetic heterostructures and diluted magnetic semiconductors of IV and III-V groups

We present the first-principles calculations of digital magnetic heterostructures Si/M, Ge/M. GaAs/M, GaSb/M, GaN/M and GaN/M (50%) with M=Cr, Mn, Fe, and Co. The interaction between magnetic dopants results in a wide spin-polarized two-dimensional band inside the gap. It is found that beginning occupation of the minority-spin band greatly increases the energy of the ferromagnetic (FM) state and leads, as a rule, to the antiferromagnetic (AFM) spin ordering. This mechanism causes transition to the AFM state, when interaction between magnetic atoms is too strong, and defines the optimum of Curie temperature as a function of transition element concentration in magnetic layers.     

Origin of ferromagnetism via hole doping in SnO2: First-principles calculation

First-principles calculations are carried out in order to find the ferromagnetism dependence on the number of holes substituted for Sn sites. The results show that strong localization of defect states of the p bands of the oxygen atoms near the dopants favors high-spin states and local moment formation. These states appear to be ferromagnetically coupled with a rather long-range magnetic interaction, resulting in a half-metallic ferromagnetic ground state for the whole systems. Analysis of the total energies indicates that the induced well-confined ferromagnetism in the oxygen p orbitals due to hole doping is quite possible and easily controlled in these systems, which indicate a new way to develop a half-metallic ferromagnet in nonmagnetic d⁰ oxides.     

The role of Co impurities and oxygen vacancies in the ferromagnetism of Co-doped SnO2: GGA and GGA+U studies

The electronic structure and ferromagnetic stability of Co-doped SnO₂ are studied using the first-principle density functional method within the generalized gradient approximation (GGA) and GGA+U schemes. The addition of effective U_Co transforms the ground state of Co-doped SnO₂ to insulating from half-metallic and the coupling between the nearest neighbor Co spins to weak antimagnetic from strong ferromagnetic. GGA+U_Co calculations show that the pure substitutional Co defects in SnO₂ cannot induce the ferromagnetism. Oxygen vacancies tend to locate near Co atoms. Their presence increases the magnetic moment of Co and induces the ferromagnetic coupling between two Co spins with large Co-Co distance. The calculated density of state and spin density distribution calculated by GGA+U_Co show that the long-range ferromagnetic coupling between two Co spins is mediated by spin-split impurity band induced by oxygen vacancies. More charge transfer from impurity to Co-3d states and larger spin split of Co-3d and impurity states induced by the addition of U_Co enhance the ferromagnetic stability of the system with oxygen vacancies. By applying a Coulomb U_O on O 2 s orbital, the band gap is corrected for all calculations and the conclusions derived from GGA+U_Co calculations are not changed by the correction of band gap.     

How to make semiconductors ferromagnetic: a first course on spintronics

The rapidly developing field of ferromagnetism in diluted magnetic semiconductors, where a semiconductor host is magnetically doped by transition metal impurities to produce a ferromagnetic semiconductor (e.g. Ga_1−xMn_xAs with x≈1-10%), is discussed with the emphasis on elucidating the physical mechanisms underlying the magnetic properties. Recent key developments are summarized with critical discussions of the roles of disorder, localization, band structure, defects, and the choice of materials in producing good magnetic quality and high Curie temperature. The correlation between magnetic and transport properties is argued to be a crucial ingredient in developing a full understanding of the properties of ferromagnetic semiconductors.     

Interplay of local structure and magnetism in Co-doped TiO2 anatase

We report ab initio density-functional theory investigations on the local structure and magnetization of Co ions doped in TiO₂ anatase. The calculated formation energy of the pair of substitutional Co ions indicates that they have a tendency to cluster; but clustering has no noticeable effect on the low-spin state of Co. The interstitial Co, which is energetically unstable in reference to bulk cobalt, is found to be strongly attracted to a substitutional Co, and even more strongly to a substitutional Co pair. Interestingly, in a one-to-one binding, the interstitial Co enhances the magnetization of the two; whereas in a one-to-two binding, it destroys the magnetic moment of the substitutional Co pair and therefore reduces the average magnetic moment of Co ions. Our results could explain the strong sample-to-sample variability of the magnetic moment of Co measured in experiments. The magnetic interaction between substitutional and interstitial Co is discussed with bonding analysis.     

Effect of impurity clustering on ferromagnetism in dilute magnetic semiconductors

We establish a model to investigate the effect of clustering of impurities on the ferromagnetism in dilute magnetic semiconductors (DMS). The Curie temperature Tc is calculated by the mean-field theory on a lattice with randomly distributed clusters of magnetic impurities which are interacting with each other by carrier mediated RKKY exchange coupling together with the nearest-neighbor (NN) direct exchange interaction. We consider different types and sizes of the clusters and find that the clustering of impurities can either enhance or reduce Tc, depending on the type and strength of the NN exchange interaction. If the NN interaction is antiferromagnetic and strong compared with the RKKY interaction, the clustering will reduce Tc. On the other hand, if it is ferromagnetic interaction or weak antiferromagnetic one, the clustering can enhance Tc. The trend of enhancing Tc is magnified if the average size of clusters increases. The clustering also changes the distribution of polarizations of impurities. The obtained results provide natural explanations on the fact that the ferromagnetism of DMS samples depends on the preparing and annealing processes even though the density of the magnetic impurities is kept the same.     

First-principle study of magnetism in Co-doped SnO2

The effects of Co dopants and oxygen vacancies on the electronic structure and magnetic properties of the Co-doped SnO₂ are studied by the first-principle calculations in full-potential linearized augmented plane wave formalism within generalized gradient approximations. The Co atoms favorably substitute on neighboring sites of the metal sublattice. Without oxygen vacancies, the Co atoms are at low spin state independent of concentration and distribution of Co atoms, and only the magnetic coupling between nearest-neighbor Co atoms is ferromagnetic through direct exchange and super-exchange interaction. Oxygen vacancies tend to locate near the Co atoms. Their presence strongly increases the local magnetic moments of Co atoms, which depend sensitively on the concentration and distribution of Co atoms. Moreover, oxygen vacancies can induce the long-range ferromagnetic coupling between well-separated Co atoms through the spin-split impurity band exchange mechanism. Thus the room temperature ferromagnetism observed experimentally in the Co-doped SnO₂ may originate from the combination of short-range direct exchange and super-exchange interaction and the long-range spin-split impurity band exchange model.     

Electronic States and Spatial Charge Distribution of Single Mn Impurity in Diluted Magnetic Semiconductors

The electronic and magnetic properties as well as the spatial charge distribution of single Mn impurity in III--V diluted magnetic semiconductors are obtained when the degeneracy of the p orbits contributed from the four nearest-neighbouring As(N) atoms is taken into account. We show that in the ground state, the Mn spin is strongly antiferromagnetically coupled to the surrounding As(N) atoms when the p-d hybridization V_pd is large and both the hole level E_v and the impurity level E_d are close to the Fermi energy. The spatial charge distribution of the Mn acceptor in the (110) plane is non-spherically symmetric, in good agreement with the recent STM images.     

Magnetic and transport properties of Mn-doped Bi2Se3 and Sb2Se3

We report on the single crystal growth and thermoelectric and magnetic properties of Mn-doped Bi₂Se₃ and Sb₂Se₃ single crystals prepared by the temperature gradient solidification method. The composition and crystal structure were determined using electron probe microanalysis and θ–2θ powder X-ray diffraction studies, respectively. The lattice constants of several percent Mn-doped Bi₂Se₃ and Sb₂Se₃ were slightly smaller than those of the undoped sample due to the smaller Mn atomic radius (1.40 Å) than those of Bi (1.60 Å) and Sb (1.45 Å). Mn-doped Bi₂Se₃ and Sb₂Se₃ showed spin-glass and paramagnetic properties, respectively.     

Defect-Bound Carrier Mediated Room-Temperature Ferromagnetism in Co-Doped ZnO Powders

We prepare pure single-phase Co：ZnO powders introducing controllable interstitial Zni by Zn vapour annealing. The as-ground powder shows that no room-temperature ferromagnetism （RT-FM） exists, while the Zn vapour treated samples exhibit unambiguous RT-FM with a maximum magnetic moment of 0.2μB/Co. The FM of Co：ZnO strongly depends on the Zn diffusion process, suggesting that not only carriers but also Zni defects play an important role in mediating FM in diluted magnetic semiconductors. A new core-shell model is proposed to interpret the mixture behaviour of FM and paramagnetism observed in the Zn vapour annealed Co：ZnO powders.     

Origin of Room-Temperature Ferromagnetism for Cobalt-Doped ZnO Diluted Magnetic Semiconductor

The pure single phase of Zn0.95 Co0.05 O bulks is successfully prepared by solid-state reaction method. The effects of annealing atmosphere on room-temperature ferromagnetic behaviour for the Zn0.95 Co0.05 O bulks are investigated. The results show that the air-annealed samples has similar weak ferromagnetic behaviour with the as-sintered samples, but the obvious ferromagnetic behaviour is observed for the samples annealed in vacuum or Ar/H2 gas, indicating that the strong ferromagnetism is associated with high oxygen vacancies density. High saturation magnetization Ms = 0.73μg/Co and coercivity Hc = 233.8 Oe are obtained for the Ar/H2 annealed samples with pure single phase structure. The enhanced room-temperature ferromagnetic behaviour is also found in the samples with high carrier concentration controlled by doping interstitials Zn （Zni）.     

Ferromagnetism from Co-Doped ZnO Nanocantilevers above Room Temperature

At low temperature （400℃）, chemical vapour deposition （CVD） is employed to make comb-like Co-doped ZnO nanocantilever arrays （NAs）. The magnetization curves of the as-synthesized Co-doped ZnO NAs indicate the existence of above-room-temperature ferromagnetism （ARTFM） （Curie temperature, Tc 〉 300 K） whereas undoped ZnO NAs does not. The corresponding ferromagnetic source mechanism is discussed, in which defects play an important role due to the strong green light emission.     

Deep defects generated in n-conducting ZnO:TM thin films

The ferromagnetism in highly transparent and intrinsically n-type conducting zinc oxide doped with 3d transition metals (TM), is predicted to be defect mediated. We investigate the generation of deep defects in n-conducting 1 μm thick ZnO:TM films (TM=Co, Mn, Ti) with a nominal TM content of 0.02, 0.20 and 2.00 at.% grown by pulsed laser deposition on a-plane sapphire substrates using deep level transient spectroscopy. We find that a defect level is generated, independent of the TM content, located 0.31 and 0.27 eV below the conduction band minimum of ZnO:Mn and ZnO:Ti, respectively. Different defect levels are generated in dependence on the Co content in ZnO:Co. This work shows that an optimization of defect-related ferromagnetism in n-conducting ZnO:TM thin films will only be possible if the preparation sensitive formation of deep defects is controlled in the same time.     

Theory of carrier mediated ferromagnetism in dilute magnetic oxides

We analyze the origin of ferromagnetism as a result of carrier mediation in diluted magnetic oxide semiconductors in the light of the experimental evidence reported in the literature. We propose that a combination of percolation of magnetic polarons at lower temperature and Ruderman-Kittel-Kasuya-Yosida ferromagnetism at higher temperature may be the reason for the very high critical temperatures measured (up to ∼700 K).     

Room-Temperature Ferromagnetism of Co-Doped CeO2 Thin Films on Si（111） substrates

Using Co2O3 as the Co source, doped cerium oxide thin films with the composition of Ce0.97C00.03O2-δ （CCO） are deposited on Si（111） and glass substrates by pulse laser deposition technique. X-ray diffraction reveals that CCO films with （111） preferential orientation are grown on Si, while the fihn on glass is polycrystalline with nanocrystal. X-ray photoelectron spectroscopy shows that the （Jo displaces the （;e atom and exists in high spin state rather than low spin state, which contributes to the room-temperature ferromagnetism confirmed by vibration sample magnetometer. I~ilms on Si and glass are different in ferromagnetism, which is believed to be induced by different film microstructures. Based on these results, the possible ferromagnetism in this insulating film is discussed. Anyway, successful fabrication of CCO films with room-temperature ferromagnetism on Si substrates is of great importance in both technological and theoretical aspects.