Theoretical study of the magnetic interaction of Cr-doped ZnO with and without vacancies

First-principles density-functional theory (DFT) calculations have been performed to study the magnetic properties of ZnO:Cr with and without vacancies. The results indicate that the doping of Cr in ZnO induces obvious spin polarization around the Fermi level and a total magnetic moment of 3.77μ_B. The ferromagnetism (FM) exchange interaction between Cr atoms is short-ranged and decreases with increasing Cr separation distance. It is suggested that the FM state is not stable with low concentration of Cr. The presence of O vacancies can make the half-metallic FM state of the system more stable, so that higher Curie temperature ferromagnetism may be expected. Nevertheless, Zn vacancies can result in the FM stability decreasing slightly. The calculated formation energy shows that V_Zn+Cr_Zn complex forms spontaneously under O-rich conditions. However, under Zn-rich conditions, the complex of V_O+Cr_Zn forms more easily. Thus, ZnO doped with Cr may exhibit a concentration of vacancies that influence the magnetic properties.     

Production of bulk dilute ferromagnetic semiconductor by mechanical milling

We tried to prepare the bulk dilute ferromagnetic semiconductor (DMS) by mechanical milling (MM). Experimental results were as following: (1) The observation of X-ray diffraction and transmitting electron microscopy showed that the particle diameter of host ZnO powder were reduced to about 10 nm by MM. (2) The MM for the mixtures of V₂O₅/ZnO or γ-Fe₂O₃/ZnO realizes the V- or Fe-doped ZnO nano-powders. (3) The values of magnetization under the field of 5 kOe were nearly saturated to 0.8×10⁻³ to 3×10⁻³ μ_B/V-ion for V_xZn_1−xO (x=0.05, 0.1 and 0.2), and 0.2–0.3 μ_B/Fe-ion for Fe_xZn_1−xO (x=0.05 and 0.1) at room temperature. The above results show that the ferromagnetic DMS powder of V_xZn_1−xO and Fe_xZn_1−xO were successfully prepared by MM method.     

Carrier-mediated ferromagnetism in N co-doped (Zn, Mn)O-based diluted magnetic semiconductors

Mn-doped ZnO is anti-ferromagnetic spin glass state, however, it becomes half-metallic ferromagnets upon hole doping. In this Letter we report a theoretical study of (Zn, Mn)O system codoped with N, and show that this codoping can change the ground state from anti-ferromagnetic to ferromagnetic. We have carried out the first-principles electronic structure calculations and report total energy to estimate whether the ferromagnetic state was stable or not. Our approach is based on the spin-polarized relativistic Korringa–Kohn–Rostoker (SPR–KKR) density functional theoretical (DFT) method, within the coherent potential approximation (CPA). Self-consistent electronic structure calculations were performed within the local density approximation, using the Vosko–Wilk–Nusair parameterization of the exchange-correlation energy functional. Our results for energy difference between ferromagnetic sate and spin glass state as well as their dependence on concentrations were presented and discussed.     

Ferromagnetism dependence on hole carriers in polycrystalline silicon films co-doped with Mn and B

Polycrystalline Si_0.96Mn_0.04:B films were prepared by cosputtering deposition followed by rapid thermal annealing for crystallization. The films are ferromagnetic with Curie temperatures of about 250 K. Through the approach of microwave plasma enhanced chemical vapor deposition, the films were treated by hydrogen plasma and boron plasma. After the plasma treatments, the structural properties of the films did not change, while both the saturation magnetization and hole concentration in the films changed. The correlation between the magnetic properties and the transport properties of the Si_0.96Mn_0.04:B films suggests that free hole carriers play an important role in Si:Mn diluted magnetic semiconductors.     

Giant magnetic moments in dilute magnetic semiconductors

The concentration dependence of the specific magnetic moment value at room temperature in dilute semiconductor titanium oxides doped with either Co or Fe has been investigated. This value was found to increase sharply at small concentrations of magnetic impurity. The magnetic moment of 22.9 μ_B per impurity atom has been revealed for TiO₂ doped with 0.15 at% Co, not yet reported in any semiconductor oxide systems. We conclude the observed giant magnetic moments are caused by the crystal lattice polarization at small impurity concentrations. The comparison with published data point to different types of the magnetization concentration dependence for various semiconductor matrixes that is probably related to the dielectric permittivity of the environment.     

Phenomenological band structure model of magnetic coupling in semiconductors

A unified band structure model is proposed to explain the magnetic ordering in Mn-doped semiconductors. This model is based on the p-d and d-d level repulsions between the Mn ions and host elements and can successfully explain magnetic ordering observed in all Mn doped II-VI and III-V semiconductors such as CdTe, GaAs, ZnO, and GaN. The model can also be used to explain the interesting behavior of GaMnN, which changes from ferromagnetic ordering to antiferromagnetic ordering as the Mn concentration increases. This model, therefore, is useful to provide a simple guideline for future band structure engineering of magnetic semiconductors.     

Influence of magnetic quantization on the Einstein relation in non-linear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestion for experimental determination

In this paper, we have investigated the Einstein relation for the diffusivity-to-mobility ratio (DMR) under magnetic quantization in non-linear optical materials on the basis of a newly formulated electron dispersion law by considering the crystal field constant, the anisotropies of the momentum-matrix element and the spin-orbit splitting constant, respectively, within the frame work of k·p formalism. The corresponding result for the three-band model of Kane (the conduction electrons of III-V, ternary and quaternary compounds obey this model) forms a special case of our generalized analysis. The DMR under magnetic quantization has also been investigated for II-VI (on the basis of Hopfield model), bismuth (using the models of McClure and Choi, Cohen, Lax and parabolic ellipsoidal, respectively), and stressed materials (on the basis of model of Seiler et al.) by formulating the respective electron statistics under magnetic quantization incorporating the respective energy band constants. It has been found, taking n-CdGeAs₂, n-Hg_1−xCd_xTe, p-CdS, and stressed n-InSb as examples of the aforementioned compounds, that the DMR exhibits oscillatory dependence with the inverse quantizing magnetic field due to Subhnikov de Haas (SdH) effect with different numerical values. The DMR also increases with increasing carrier degeneracy and the nature of oscillations are totally dependent on their respective band structures in various cases. The classical expression of the DMR has been obtained as a special case from the results of all the materials as considered here under certain limiting conditions, and this compatibility is the indirect test of our generalized formalism. In addition, we have suggested an experimental method of determining the DMR for degenerate materials under magnetic quantization having arbitrary dispersion laws. The three applications of our results in the presence of magneto-transport have further been suggested.     

Development of a magnetic measurement device for thin ribbon samples

This paper presents a magnetic measurement device for thin ribbon samples, which are produced by rapid cooling technique. This device enables us to measure magnetic properties easily by only inserting a ribbon sample into a sample holder. The sample holder was made by bakelite to fix any width sample. A long solenoid coil was used to generate a uniform magnetic field and the sample holder was placed at the mid part of the solenoid. The magnetic field strength was measured using a shunt resistor and the magnetic flux density and magnetization in sample ribbons were evaluated by using search coils. The accuracy of measurement was verified with an amorphous metal ribbon sample. Next, we have measured magnetic properties of some magnetic shape memory alloys, which have different compositions. The measured results are compared and we clarified the effect of Sm contents on the magnetic properties.     

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.     

Dilute magnetic semiconductors based on wide bandgap SiO2 with and without transition metal elements

Material designs based on the first principle calculations of electronic structures are proposed for α-quartz SiO₂-based dilute magnetic semiconductors. The incorporation of transition metals (TMs) into Si sites and of the non-TM atoms into O sites are treated for various concentrations. At temperatures higher than room temperature, most of the TM-doped SiO₂ have no magnetism, yet Si_1−xMn_xO₂ might achieve the ferromagnetism. The substitution of O by non-TM atoms as C or N also induces the magnetism in the host. However, while the N's substitution induces the ferromagnetism, C's substitution causes an anti-ferromagnetic behavior in the host material SiO₂.     

Ferromagnetic properties of Fe-substituted ZnO-based magnetic semiconductor

The diluted magnetic semiconductor Zn_1−x⁵⁷Fe_xO (x=0.01, 0.02, 0.03) compounds were prepared by the solid-state reaction method. The crystal structure of _Zn0.97⁵⁷_Fe0.03O${\mathrm{Zn}}_{0.97}{}^{57}{\mathrm{Fe}}_{0.03}\mathrm{O}$ at room temperature is determined to be a hexagonal structure of P6₃mc with lattice constants a₀=3.252 Å and c₀=5.205 Å by Rietveld refinement. The Bragg factors R_B and R_F were determined as 3.23% and 2.81%. From the inverse susceptibility versus T curve, the paramagnetic Curie temperature is found to be 2.7 K and effective moment is found to be 4.01 μ_B, thereby suggesting that the exchange interactions between Fe ions are ferromagnetic. Mössbauer spectra of _Zn0.97⁵⁷_Fe0.03O${\mathrm{Zn}}_{0.97}{}^{57}{\mathrm{Fe}}_{0.03}\mathrm{O}$ have been taken at various temperatures ranging from 4.2 to 295 K. Mössbauer spectrum for _Zn0.97⁵⁷_Fe0.03O${\mathrm{Zn}}_{0.97}{}^{57}{\mathrm{Fe}}_{0.03}\mathrm{O}$ at 4.2 K has shown ferromagnetic phase (sextet), and the spectra were fitted based on a random distribution model of Fe ions.     

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).     

Magnetic field-induced ferromagnetism in iron oxide microspheres

A magnetic field of 12 T was applied during the annealing of amorphous α-Fe₂O₃ microspheres. The authors demonstrate that magnetic field processing leads to the formation of γ-Fe₂O₃ phases in the microspheres, and the field-treated microspheres exhibit typical room-temperature ferromagnetic behavior, whereas non-field-heated sample presents paramagnetism. The improvement in magnetic properties is considered to be a result of magnetic field-induced transformation from α-Fe₂O₃ to γ-Fe₂O₃.     

High temperature magnetic ordering in La2RuO5

Magnetic susceptibility, heat capacity and electrical resistivity measurements have been carried out on a new ruthenate, La₂RuO₅ (monoclinic, space group P2₁/c) which reveal that this compound is a magnetic semiconductor with a high magnetic ordering temperature of 170 K. The entropy associated with the magnetic transition is 8.3 J/mol K close to that expected for the low spin (S=1) state of Ru⁴⁺ ions. The low temperatures specific heat coefficient γ is found to be nearly zero consistent with the semiconducting nature of the compound. The magnetic ordering temperature of La₂RuO₅ is comparable to the highest known Curie temperature of another ruthenate, namely, metallic SrRuO₃, and in both these compounds the nominal charge state of Ru is 4+.     

Oxygen Recovery in Hf Oxide Films Fabricated by Sputtering

The chemical structure of ultrathin Hf oxide films （〈 10 nm） fabricated by a standard sputtering method is investigated using x-ray spectroscopy and Rutherford backseattering spectroscopy. According to the experiments, oxygen species are impacted to the HfO2/Si interface during the initial sputtering, and then released back to the upper HfO2 region driven by the oxygen concentration grads. A vacuum annealing can greatly enhance this recovery process. Additionally, significant SiO2 reduction in the interface is observed after the vacuum annealing for the thick HfO2 films in our experiment. It might be an effective method to confine the interracial layer thickness by sputtering thick HfO2 in no-oxygen ambient.     

Charge carriers and mobility of Cu-Ti ferrite

The concentration and drift mobility of charge carriers in Cu_1–x Ti _x Fe₂O₄ ferrite are calculated, over a wide range of temperatures (300–773 K), employing d.c. conductivity and thermoelectric power data. With increasing temperature the concentration of charge carriers decreases whilst the drift mobility exhibits an exponential increase. Over the above-mentioned temperature range, the obtained density of charge carriers varies between 10²¹ and 10²² cm^–3 whereas the drift mobility has values between 10^–8 and 10^–4 cm²/V s. The results are discussed on the basis of a small-polaron hopping conduction. The activation of the d.c. conductivity has been attributed to the thermal activation of the mobility.     

Ferromagnetic spin ordering in disordered Sr2FeMoO6 films

Epitaxial films of Sr₂FeMoO₆ were grown on SrTiO₃ (100) substrates by pulsed laser deposition; optimised growth conditions give a saturation magnetization of 4.0μ_B implying a high degree of B-site ordering. The films show very high crystallinity and smooth surfaces. We have compared the B-site disorder in the films with saturation magnetization and show that the rate of suppression with disorder is lower than that suggested by Monte Carlo simulations, suggesting the ferromagnetic coupling in the Fe/Mo sublattices.     

Photoluminescence investigation of ferromagnetic Ga1−xMnxN layers with GaN templates grown on sapphire (0 0 0 1) substrates

We have investigated the temperature and composition dependent photoluminescence (PL) spectra in Ga_1−xMn_xN layers (where x ≈ 0.1-0.8%) grown on sapphire (0 0 0 1) substrates using the plasma-enhanced molecular beam epitaxy technique. The efficient PL is peaked in the red (1.86 eV), yellow (2.34 eV), and blue (3.29 eV) spectral range. The band-gap energy of the Ga_1−xMn_xN layers decreased with increasing temperature and manganese composition. The band-gap energy of the Ga_1−xMn_xN layers was modeled by the Varshni equation and the parameters were determined to be α = 2.3 × 10⁻⁴, 2.7 × 10⁻⁴, 3.4 × 10⁻⁴ eV/K and β = 210, 210, and 230 K for the manganese composition x = 0.1%, 0.2%, and 0.8%, respectively. As the Mn concentration in the Ga_1−xMn_xN layers increased, the temperature dependence of the band-gap energy was clearly reduced.     

Localization of nonequilibrium current carriers close to Cr ions in ZnSe:Cr single crystals

The photoluminescence (PL) of Cr-doped ZnSe single crystals is investigated in a temperature interval from 83 up to 297 K and in a wavelengths region from 440 up to 2700 nm. The doping was carried out during a high-temperature annealing of ZnSe crystals in CrSe vapors and in chrome chlorides medium. It is revealed that the doping results in an appearance of both luminescence bands located at 0.54, 0.97, and 2.15 μm and edge luminescence bands located at 454, 457, and 460 nm at 83 K. It is shown that the PL bands located at 457 and 460 nm are caused by the radiative recombination with the participation of holes located on hydrogen-like orbits close to Cr⁺ centers, having a binding energy of 99 meV. The excitons bound with centers responsible for the radiation located at 0.54 μm and having a binding energy of 65-68 meV are considered. The energy of a lattice relaxation at recharge of centers responsible for green radiation is estimated and equals 40-170 meV.