High temperature ferromagnetism of the vacuum-annealed (In1−xFex)2O3 powders

(In_1−xFe_x)₂O₃ (x = 0.02, 0.05, 0.2) powders were prepared by a solid state reaction method and a vacuum annealing process. A systematic study was done on the structural and magnetic properties of (In_1−xFe_x)₂O₃ powders as a function of Fe concentration and annealing temperature. The X-ray diffraction and high-resolution transmission electron microscopy results confirmed that there were not any Fe or Fe oxide secondary phases in vacuum-annealed (In_1−xFe_x)₂O₃ samples and the Fe element was incorporated into the indium oxide lattice by substituting the position of indium atoms. The X-ray photoelectron spectroscopy revealed that both Fe²⁺ and Fe³⁺ ions existed in the samples. Magnetic measurements indicated that all samples were ferromagnetic with the magnetic moment of 0.49-1.73 μ_B/Fe and the Curie temperature around 783 K. The appearance of ferromagnetism was attributed to the ferromagnetic coupling of Fe²⁺ and Fe³⁺ ions via an electron trapped in a bridging oxygen vacancy.     

A close correlation between induced ferromagnetism and oxygen deficiency in Fe doped In2O3

We report on the reversible manipulation of room temperature ferromagnetism in Fe (5%) doped In₂O₃ polycrystalline magnetic semiconductor. The X-ray diffraction and photoemission measurements confirm that the Fe ions are well incorporated into the lattice, substituting the In³⁺ ions. The magnetization measurements show that the host In₂O₃ has a diamagnetic ground state, while it shows weak ferromagnetism at 300 K upon Fe doping. The as-prepared sample was then sequentially annealed in hydrogen, air, vacuum and finally in air. The ferromagnetic signal shoots up by hydrogenation as well as vacuum annealing and bounces back upon re-annealing the samples in air. The sequence of ferromagnetism shows a close inter-relationship with the behavior of oxygen vacancies (V_o). The Fe ions tend to a transform from 3+ to 2+ state during the giant ferromagnetic induction, as revealed by photoemission spectroscopy. A careful characterization of the structure, purity, magnetic, and transport properties confirms that the ferromagnetism is due to neither impurities nor clusters but directly related to the oxygen vacancies. The ferromagnetism can be reversibly controlled by these vacancies while a parallel variation of carrier concentration, as revealed by resistance measurements, appears to be a side effect of the oxygen vacancy variation.     

Effect of hydrogenation vs. re-heating on intrinsic magnetization of Co doped In2O3

Influence of Co doping for In in In₂O₃ matrix has been investigated to study the effect on magnetic vs. electronic properties. Rietveld refinement of X-ray diffraction patterns confirmed formation of single phase cubic bixbyite structure without any parasitic phase. Photoelectron spectroscopy and refinement results further revealed that dopant Co²⁺ ions are well incorporated at the In³⁺ sites in In₂O₃ lattice and also ruled out formation of cluster in the doped samples. Magnetization measurements infer that pure In₂O₃ is diamagnetic and turns to weak ferromagnetic upon Co doping. Hydrogenation further induces a huge ferromagnetism at 300 K that vanishes upon re-heating. Experimental findings confirm the induced ferromagnetism to be intrinsic, and the magnetic moments to be associated with the point defects (oxygen vacancies V_o) or bound magnetic polarons around the dopant ions.     

Magnetism on Mg1−xZnxCyNi3

The magnetic phase diagram for Mg_1−xZn_xC_yNi₃ has been tentatively constructed based on magnetization and muon spin relaxation (μSR) measurements. The superconducting phase was observed to fade as x (y) increases (decreases). The low y samples show early stages of long-range ferromagnetism, or complete long-range ferromagnetism. In the phase diagram, the ferromagnetic phase exists in addition to the superconducting phase, suggesting that there is some correlation between superconductivity and ferromagnetism, even though the coexistence of ferromagnetism and superconductivity is not observed from the μSR measurements down to 20 mK for the superconducting sample (T_c=2.5 K, (x, y)=(0, 0.9)).     

Room-temperature ferromagnetism in Sn1−xMnxO2 nanocrystalline thin films prepared by ultrasonic spray pyrolysis

Sn_1−xMn_xO₂ (x=0.01-0.05) thin films were synthesized on quartz substrate using an inexpensive ultrasonic spray pyrolysis technique. The influence of doping concentration and substrate temperature on structural and magnetic properties of Sn_1−xMn_xO₂ thin films was systematically investigated. X-ray diffraction (XRD) studies of these films reflect that the Mn³⁺ ions have substituted Sn⁴⁺ ions without changing the tetragonal rutile structure of pure SnO₂. A linear increase in c-axis lattice constant has been observed with corresponding increase in Mn concentration. No impurity phase was detected in XRD patterns even after doping 5 at% of Mn. A systematic change in magnetic behavior from ferromagnetic to paramagnetic was observed with increase in substrate temperature from 500 to 700 °C for Sn_1−xMn_xO₂ (x=0.01) films. Magnetic studies reveal room-temperature ferromagnetism (RTFM) with 3.61×10⁻⁴ emu saturation magnetization and 92 Oe coercivity in case of Sn_1−xMn_xO₂ (x=0.01) films deposited at 500 °C. However, paramagnetic behavior was observed for the films deposited at a higher substrate temperature of 700 °C. The presence of room-temperature ferromagnetism in these films was observed to have an intrinsic origin and could be obtained by controlling the substrate temperature and Mn doping concentration.     

Microstructure, magnetic and optical properties of sputtered polycrystalline ZnO films with Fe addition

Microstructure, magnetic and optical properties of polycrystalline Fe-doped ZnO films fabricated by cosputtering with different Fe atomic fractions (x_Fe) have been examined systematically. Fe addition could affect the growth of ZnO grains and surface morphology of the films. As x_Fe is larger than 7.0%, ZnFe₂O₄ grains appear in the films. All the films are ferromagnetic. The ferromagnetism comes from the ferromagnetic interaction activated by defects between the Fe ions that replace Zn ions. The average moment per Fe ion reaches a maximum value of 1.61 μ_B at x_Fe = 4.8%. With further increase in x_Fe, the average moment per Fe ion decreases because the antiferromagnetic energy is lower than the ferromagnetic one due to the reduced distance between the adjacent Fe ions. The optical band gap value decreases from 3.245 to 3.010 eV as x_Fe increases from 0% to 10%. Photoluminescence spectra analyses indicate that many defects that affect the optical and magnetic properties exist in the films.     

Effect of Sr concentration on microstructure and magnetic properties of (Ba1−xSrx)(Ti0.3Fe0.7)O3 ceramics

Fe-doped (Ba_1−xSr_x)TiO₃ ceramics were prepared by solid-state reaction, and ferromagnetism was realized at room temperature. The microstructure and magnetism were modified by the Sr concentration control (0≤x≤75 at%) at a fixed Fe concentration, and the relevant magnetic exchange mechanism was discussed. All the samples are shown to have a single perovskite structure. When increasing the Sr concentration, the phase structure is transformed from a hexagonal perovskite into a cubic perovskite, with a monotonic decrease in lattice parameters induced by ionic size effect. The room-temperature ferromagnetism is expected to originate from the super-exchange interactions between Fe³⁺ on pentahedral and octahedral Ti sites mediated by the O²⁻ ions. The increase in Sr addition modifies two main influencing factors in magnetic properties: the ratio of pentahedral to octahedral Fe³⁺ and the concentration of oxygen vacancies, leading to a gradually enhanced saturation magnetization. The highest value, obtained for Fe-doped (Ba_0.25Sr_0.75)TiO₃, is an order of magnitude higher than that of the Fe-doped BaTiO₃ system with similar Fe concentration and preparation conditions, which may indicate (Ba_1−xSr_x)TiO₃ as a more suitable matrix material for multiferroic research.     

Magnetic properties and Griffiths singularity in La0.45Sr0.55 Mn1−xCoxO3

The magnetic properties and the Griffiths singularity were investigated in Mn-site doped manganites of La_0.45Sr_0.55Mn_1−xCo_xO₃ (x=0, 0.05, 0.10 and 0.15) in this work. The parent sample La_0.45Sr_0.55MnO₃ undergoes a paramagnetic-ferromagnetic transition at T_C=290 K and a ferromagnetic-antiferromagnetic transition at T_N=191 K. The doping of Co ions enhances the ferromagnetism and suppresses the antiferromagnetism. The enhanced ferromagnetism results from the fact that the Co doping enhances the Mn³⁺-Mn⁴⁺ double-exchange interaction and induces the Co²⁺-Mn⁴⁺ ferromagnetic superexchange interaction. Detailed investigation on the magnetic behavior above T_C exhibits that the Griffiths singularity takes place in this series of Mn-site doped compounds. The correlated disorder induced by the Co ionic doping, together with the phase competition from the ferromagnetic and the antiferromagnetic interactions among Mn ions, is responsible for the Griffiths singularity.     

Structural and magnetic properties of Mg(In2−xMnx)O4 system

We synthesized the Mn-doped Mg(In_2−xMn_x)O₄ oxides with 0.03?x?0.55 using a solid-state reaction method. The X-ray diffraction patterns of the samples were in a good agreement with that of a distorted orthorhombic spinel phase. Their lattice parameters and unit-cell volumes decrease with x due to the substitution of the smaller Mn³⁺ ions to the larger In³⁺ ions. The undoped MgIn₂O₄ oxide presents diamagnetic signals for 5 K?T?300 K. The M(H) at T=300 K reveals a fairly negative-sloped linear relationship. Neither magnetic hysteresis nor saturation behavior was observed in this parent sample. For the Mn-doped samples, however, positive magnetization were observed between 5 and 300 K even if the x value is as low as 0.03. The mass susceptibility enhances with Mn content and it reaches the highest value of 1.4×10⁻³ emu/g Oe (at T=300 K) at x=0.45. Furthermore, the Mn-doped oxides with x=0.06 and 0.2, respectively, exhibit nonlinear magnetization curves and small hysteretic loops in low magnetic fields. Susceptibilities of the Mn-doped samples are much higher than those of MnO₂, Mn₂O₃ oxides, and Mn metals. These results show that the oxides have potential to be magnetic semiconductors.     

Possible room-temperature ferromagnetism in SnO2 nanocrystalline powders with nonmagnetic K doping

Sn_1 − xK_xO₂ nanocrystalline powders were synthesized by the sol-gel method. The room-temperature ferromagnetism was observed in K-doped samples, and the saturation magnetization increases with the K concentration. It indicates the ferromagnetism induced by holes injecting is possible. First-principles calculations were employed to analyze the effect of defects on the structural and magnetic properties. Taking into account the structural and valence state characterization, the inhomogeneous distribution of dopants and the holes compensation effect of K and H interstitials in crystal were thought to play important roles in reducing the magnetic moments in samples.     

Effect of Sn-doping on the structural,magnetic and magnetocaloric properties of La0.67Ba0.33Mn1−xSnxO3 compounds

Magnetocaloric effect (MCE) in fine-grained perovskite manganites of the type La_0.67Ba_0.33Mn_1−xSn_xO₃ (x=0.05, 0.1 and 0.15) were prepared by the solid-state method. The prepared samples remain single phase and exhibit paramagnetic to ferromagnetic phase transition (T_C) at 340, 325 and 288 K for x=0.05, 0.1 and 0.15, respectively. From the measured magnetization data of La_0.67Ba_0.33Mn_1−xSn_xO₃ compounds as a function of field (2 T), the associated magnetic entropy change close to their respective Curie temperatures and the relative cooling power (RCP) have been determined. Large MCE has been obtained in all samples and |ΔS_M|_max reached the highest value of 2.49 J/kg K at T_C (288 K) for the sample x=0.15, with H=2 T.     

Effect of 3d metal ion doping on the structure and superconductivity of (Tl0.5Pb0.5)Sr2CaCu2O7

(Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ (M=Co, Ni and Zn) have been synthesized and investigated by means of X-ray diffraction, scanning electron microscope, electrical resistivity and magnetic susceptibility measurements. X-ray diffraction patterns show that all studied samples contain the nearly single ‘1212’ phase. They crystallize in a tetragonal unit cell with a=3.8028-3.8040 Å and c=12.0748-12.1558 Å. In (Tl_0.5Pb_0.5)Sr₂Ca(Cu_2−xM_x)O₇ system (M=Co or Ni), the superconducting critical temperature T_c decreases linearly with both Co and Ni concentrations and the rate of T_c decrease is around −6.5 and −7.0 K/at%, respectively. For (Tl_0.5Pb_0.5)Sr₂Ca (Cu_2−xZn_x)O₇ system, the dependence of T_c on the Zn dopant concentration deviates from a linear behavior and the Zn substitution suppresses T_c much less (−2.5 K/at%) than the Co and Ni substitutions. The suppression in T_c in Co and Ni doped samples are attributed to the magnetic pair-breaking mechanism and the reduction in the carrier concentration. The suppression of T_c in Zn doped samples is not caused by the reduction in carrier concentration which should remain constant, but rather due to nonmagnetic pair-breaking mechanism induced by disorder as well as the filling of the local Cu d_x²−y² state due to the full d band of Zn ions.     

Influence of doping concentration on room-temperature ferromagnetism for Fe-doped BaTiO3 ceramics

Ba(Ti_1−xFe_x)O₃ ceramics (x=7, 30 and 70 at%) were prepared by solid-state reaction. All samples are single-phase with 6H-BaTiO₃-type hexagonal perovskite structure. Mössbauer spectra show all Fe atoms to be present as Fe³⁺ in BaTiO₃ lattice, occupying M1 octahedral and pentahedral sites. Room-temperature ferromagnetism is exhibited and saturation magnetization gradually decreases with increasing Fe content. The observed ferromagnetism is considered to be an intrinsic property of Ba(Ti_1−xFe_x)O₃, originating from super-exchange interactions between Fe³⁺ in different occupational sites associated with oxygen vacancies. The variation in magnetization with Fe content is related to the ratio of pentahedral to octahedral sites and oxygen vacancies.     

Room-temperature ferromagnetism in Zn1−xMnxO

In view of recent controversies on above room-temperature ferromagnetism (RTFM) in transition-metal-doped ZnO, the present paper aims to shed some light on the origin of ferromagnetism by investigating annealing effects on structure and magnetism for polycrystalline Zn_1−xMn_xO powder samples prepared by solid-state reaction method and annealed in air at different temperatures. Magnetic measurements indicate that the samples are ferromagnetic at room temperature (RTFM). Room temperature ferromagnetism has been observed in the sample annealed at a low temperature of 500 °C with a saturated magnetization (M_s) of 0.159 emu/g and a coercive force of 89 Oe. A reduction in RTFM is clearly observed in the sample annealed at 600 °C. Furthermore, the saturation magnetic moment decreases with an increase in grain size, suggesting that ferromagnetism is due to defects and/or oxygen vacancy confined to the surface of the grains. The experimental results indicate that the ferromagnetism observed in Zn_1−xMn_xO samples is intrinsic rather than associated with secondary phases.     

Electronic structure and magnetic properties of BaTi1-xMnxO3

The electronic structure and magnetic properties of polycrystalline BaTi_1-xMn_xO₃ (x = 0–0.1) compounds prepared by solid-state reactions were studied. The results revealed that the increase in Mn content (x) did not change the oxidation numbers of Ba (+2) and Ti (+4) in BaTi_1-xMn_xO₃. However, there is the change in Mn valence that Mn^3+,4+ ions coexist in the samples with x = 0.01–0.04 while Mn⁴⁺ ions are almost dominant in the samples with x = 0.06–0.1. We also point out that Mn³⁺ and Mn⁴⁺ ions substitute for Ti⁴⁺ and prefer locating in the tetragonal and hexagonal BaTiO₃ structures, respectively, in which the hexagonal phase constitutes soon as x = 0.01. Particularly, all the samples exhibit room-temperature ferromagnetism. Ferromagnetic order increases with increasing x from 0 to 0.02, but decreases as x ≥ 0.04. We think that ferromagnetism in BaTi_1-xMn_xO₃ is related to lattice defects and/or exchange interactions between Mn³⁺ and Mn⁴⁺ ions.     

Effect of Fe substitution on magnetocaloric effect in La0.7Sr0.3Mn1−xFexO3 (0.05≤x≤0.20)

We have studied the effect of Fe substitution on magnetic and magnetocaloric properties in La_0.7Sr_0.3Mn_1−xFe_xO₃ (x=0.05, 0.07, 0.10, 0.15, and 0.20) over a wide temperature range (T=10-400 K). It is shown that substitution by Fe gradually decreases the ferromagnetic Curie temperature (T_C) and saturation magnetization up to x=0.15 but a dramatic change occurs for x=0.2. The x=0.2 sample can be considered as a phase separated compound in which both short-range ordered ferromagnetic and antiferromagnetic phases coexist. The magnetic entropy change (−ΔS_m) was estimated from isothermal magnetization curves and it decreases with increase of Fe content from 4.4 J kg⁻¹ K⁻¹ at 343 K (x=0.05) to 1.3 J kg⁻¹ K⁻¹ at 105 K (x=0.2), under ΔH=5 T. The La_0.7Sr_0.3Mn_0.93Fe_0.07O₃ sample shows negligible hysteresis loss, operating temperature range over 60 K around room temperature with refrigerant capacity of 225 J kg⁻¹, and magnetic entropy of 4 J kg⁻¹ K⁻¹ which will be an interesting compound for application in room temperature refrigeration.     

Room temperature ferromagnetism behavior of Sn1−xMnxO2 powders

In this paper, we have investigated Mn-doped SnO₂ powder samples prepared by solid-state reaction method. X-ray diffraction showed a single phase polycrystalline rutile structure. The atomic content of Mn ranged from ∼0.8 to 5 at%. Room temperature M-H loops showed a ferromagnetic behavior for all samples. The ferromagnetic Sn_0.987Mn_0.013O₂ showed a coercivity H_c=545 Oe, which is among the highest reported for dilute magnetic semiconductors. The magnetic moment per Mn atom was estimated to be about 2.54 μ_B of the Sn_0.9921Mn_0.0079O₂ sample. The average magnetic moment per Mn atom sharply decreases with increasing Mn content, while the effective fraction of the Mn ions contributing to the magnetization decreases. The magnetic properties of the Sn_1−xMn_xO₂ are discussed based on the competition between the antiferromagnetic superexchange coupling and the F-center exchange coupling mechanism, in which both oxygen vacancies and magnetic ions are involved.     

Thermal stability of A-site ordered PrBaMn2O6 manganites

The crystal structure and electromagnetic properties as well as thermal stability of the A-site ordered PrBaMn₂O₆ manganites have been investigated. These samples have been prepared by using ‘two-steps’ synthesis mode. They have tetragonal structure with no tilt of MnO₆ octahedra and show ferromagnetic metal to paramagnetic semiconductor transition. The most significant structural feature of the A-site ordered manganites is that the MnO₂ sublattice is sandwiched by two types of rock-salt layers PrO and BaO. The different degree of Pr and Ba ions in the A-sublattice is revealed. The A-site ordered PrBaMn₂O₆ sample with maximum degree of the A-site order demonstrates ferromagnetic metallic to paramagnetic insulating transition with the Curie point ∼320 K. The A-site disordered Pr_0.50Ba_0.50MnO₃ sample is ferromagnetic metal below T_C≈140 K. The cation order in these compounds is stable in air up to 1300 °C. For the partly A-site ordered samples the magnetic and electronic phase separation is observed. The magnetotransport properties of the A-site ordered manganites treated under different conditions are discussed in terms of the superexchange interactions and A-site order degree.     

The important role of Mn in the room-temperature ferromagnetism of Mn-doped GaN films

Mn-doped GaN films (Ga_1−xMn_xN) were grown on sapphire (0 0 0 1) using Laser assisted Molecular Beam Epitaxy (LMBE). High-quality nanocrystalline Ga_1−xMn_xN films with different Mn concentration were then obtained by thermal annealing treatment for 30 min in the ammonia atmosphere. Mn ions were incorporated into the wurtzite structure of the host lattice by substituting the Ga sites with Mn³⁺ due to the thermal treatment. Mn³⁺, which is confirmed by XPS analysis, is believed to be the decisive factor in the origin of room-temperature ferromagnetism. The better room-temperature ferromagnetism is given with the higher Mn³⁺ concentration. The bound magnetic polarons (BMP) theory can be used to prove our room-temperature ferromagnetic properties. The film with the maximum concentration of Mn³⁺ presents strongest ferromagnetic signal at annealing temperature 950 °C. Higher annealing temperature (such as 1150 °C) is not proper because of the second phase Mn_xGa_y formation.     

Mn1−xFexIn2Se4: a new layered semiconductor system

Mn_1−xFe_xIn₂Se₄ compounds (x=0.1; x=0.7) were grown by the chemical vapor transport method. X-ray diffraction analysis data show that these compositions crystallize as different polytypes that belong to the hexagonal structure. The crystal symmetry of the sample with x=0.1 belongs to the space group Rm and for the sample with x=0.7 the space group is P6₃mc.The magnetic behavior of both samples has been investigated in the temperature range between 5 and 300 K. Spin-glass-like behavior below the freezing temperature T_f=9 K has been found for the sample with x=0.7. The sample with Fe content x=0.1 behaves as a paramagnet down to the lowest experimental measured temperature. High-temperature susceptibility data follow the Curie-Weiss law with a negative paramagnetic temperature indicating predominant antiferromagnetic interactions.Optical studies reveal that both samples (x=0.1; 0.7) are direct band gap semiconductors. The temperature dependence of the energy gap fits Varshni relation quite well.