Structure and magnetic properties of Sn1−xMnxO2

The microstructure and magnetic properties have been investigated systematically for Sn_1−xMn_xO₂ polycrystalline powder samples with x=0.02-0.08 synthesized by a solid-state reaction method. X-ray diffraction revealed that all samples are pure rutile-type tetragonal phase and the cell parameters a and c decrease monotonously with the increase in Mn content, which indicated that Mn ions substitute into the lattice of SnO₂. Magnetic measurements revealed that all samples exhibit room temperature ferromagnetism. Furthermore, magnetic investigations demonstrate that magnetic properties strongly depend on doping content, x. The average magnetic moment per Mn atom decreases with increase in the Mn content, because antiferromagnetic super-exchange interaction takes place within the neighbor Mn³⁺ ions through O²⁻ ions for the samples with higher Mn doping. Our results indicate that the ferromagnetic property is intrinsic to the SnO₂ system and is not a result of any secondary magnetic phase or cluster formation.     

Bulk Sn1−xMnxO2 magnetic semiconductors without room-temperature ferromagnetism

Polycrystalline Sn_1−xMn_xO₂ (0≤x≤0.05) diluted magnetic semiconductors were prepared by solid-state reaction method and their structural and magnetic properties had been investigated systematically. The three Mn-doped samples (x=0.01, 0.03, 0.05) undergo paramagnetic to ferromagnetic phase transitions upon cooling, but their Curie temperatures are far lower than room temperature. The magnetization cannot be attributed to any identified impurity phase. It is also found that the magnetization increases with increasing Mn doping, while the ratio of the Mn ions contributing to ferromagnetic ordering to the total Mn ions decreases.     

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.     

Structural and magnetic properties of Cu1−xMnxO nanocrystal prepared by combustion synthesis

Nanoscale Cu_1−xMn_xO powder is prepared by using the combustion synthesis technique with two different fuels. The structural properties of the powder are determined using Rietveld refinement of X-ray diffraction data, high-resolution transmission electron microscopy, and Fourier transform infrared spectroscopy, while its magnetic properties are analyzed by means of hysteresis loop and temperature dependence of magnetization. The results show that (1) the Cu_1−xMn_xO nanocrystal is of monoclinic CuO structure, with grain size of 10-30 nm varying with the type of fuel, the nitrate/fuel ratio (N/F), and the Mn concentration, the doping of Mn has a little influence on the lattice parameters; (2) when the Mn concentration is higher than 7%, a small amount of impurity phase of CuMn₂O₄ appears and annihilates the potential cation vacancies; (3) all of the samples with x≥5% exhibit low-temperature ferromagnetism with the Curie temperature of ∼90 K, which increases slightly by raising the Mn concentration; (4) the paramagnetic moment per Mn ion is around 2-4 bohr magneton above the Curie temperature, which decreases with increasing Mn concentration, implying that the nearest Mn ions are antiferromagnetically coupled and the ferromagnetic order could originate from the super-exchange of next nearest Mn ions along the [1 0 1?] direction.     

Magnetic properties of Mn-rich Rh2Mn1+xSn1−x Heusler alloys

X-ray powder diffraction and magnetization measurements have been carried out on Rh₂Mn_1+xSn_1−x (0≤x≤0.3) alloys. The alloys, which crystallize in the L2₁ structure, were found to exhibit ferromagnetic behavior. The lattice constant a at room temperature decreases with increasing x, whereas the Curie temperature T_C decreases linearly. At 5 K the magnetic moment per formula unit first increases with increasing x and then saturates for x≥0.2. The experimental results are discussed in terms of the influence of the Mn-Mn exchange interactions between the Mn atoms on the Sn and Mn sites.     

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.     

Synthesis, structural and magnetic study of polycrystalline LaNi1−xMnxO3 films

Polycrystalline double perovskite LaNi_1−xMn_xO₃ (x=0.3, 0.4, 0.5 and 0.7, which is defined as Mn03, Mn04, Mn05 and Mn07, respectively) thin films are successfully deposited on Si (1 0 0) substrates via chemical solution deposition method. Their structural and magnetic properties are measured. All the thin films are of single phase. Raman spectra indicate that relative intensity of Mn05 is stronger than that of others that can be attributed to the higher degree of B-site ordering. The low temperature magnetic moment of Mn05 is about 500 emu/cm³, which is obviously larger than that of Mn03 and Mn07 because of the long-range ordering of Mn and Ni ions in Mn05.     

First-principles study of electronic structure and magnetic properties of doped SnO2 (rutile) with single and double impurities

Using the augmented spherical wave method, the electronic structure and magnetic properties of the rutile SnO₂ doped with single and double impurities: Sn_1−xMn_xO₂, Sn_1−xW_xO₂, and Sn_1−2xMn_xW_xO₂ with x=0.0625, have been studied. The scalar-relativistic implementation with a generalized gradient approximation functional has been used for treating the effects of exchange and correlation. The ground state of Mn-, and W-doped SnO₂ systems have a total magnetic moments of 3 and 2 μ_B, respectively. The half-metallic nature appears in Sn_1−2xMn_xW_xO₂, which makes them suitable as spintronic systems with total magnetic moment of 5 μ_B. The advantages of doping SnO₂ with double impurities are investigated in this work. The total moment of the system, the local magnetic moments of the impurities, and their oxidation states are also discussed. Since there are two possible couplings between the impurities, we studied both configurations (ferromagnetic and antiferromagnetic) for double-impurities-doped SnO₂. Magnetic properties and interatomic exchange have been computed for various distances between Mn and W. The indirect exchange between double impurities has similarities with the Zener mechanism in transition metal oxides. Based on the interaction between localized moments, via hybridization between impurities orbitals with the host oxygen, a double exchange mechanism is proposed to explain the ferromagnetism of our system.     

X-ray photoelectron study of Sn1−xMnxTe semimagnetic semiconductors

X-ray photoelectron (XPS) studies of core-levels in Sn_1−xMn_xTe (x < 0.1) semimagnetic semiconductors have been performed. The spectra were acquired under UHV conditions from the clean (as-cleaved or in-situ scraped) crystal surface. The single-phase NaCl structure of the alloys studied was verified by X-ray diffraction (XRD). The structure of Sn 3d and Te 3d core-levels in SnMnTe was found fully consistent with that of SnTe. Remarkable qualitative similarity of the Mn 2p spectrum of Sn_1−xMn_xTe (x = 0.09) with the case of zinc-blende MnTe [R.J. Iwanowski, M.H. Heinonen, E. Janik, Chem. Phys. Lett. 387 (2004) 110] has been shown: (1) the same binding energies (BEs) of the main contributions to the Mn 2p_3/2 line, related to Mn²⁺ state of the bulk MnTe bond; (2) occurrence of low BE component in the Mn 2p spectrum, indicative of clean-surface species containing reduced-valence Mn ions (i.e. Mn^q+, where 0 < q < 2); (3) strong satellites of the 2p_3/2 (Mn²⁺ related) parent lines. In SnMnTe, the highest intensity ratio of the satellite to main peak (ever reported for Mn 2p photoelectron spectrum) was revealed; this was interpreted in terms of the so-called charge-transfer model.     

Optical and magnetic properties of (Ga1−xMnx)N/GaN digital ferromagnetic heterostructures

(Ga_1−xMn_x)N/GaN digital ferromagnetic heterostructures (DFHs) and (Ga_1−xMn_x)N/GaN grown on GaN buffer layers by using molecular beam epitaxy have been investigated. The photoluminescence (PL) spectra showed band-edge exciton transitions. They also showed peaks corresponding to the neutral donor-bound exciton and the exciton transitions between the conduction band and the Mn acceptor, indicative of the Mn atoms acting as substitution. The magnetization curves as functions of the magnetic field at 5 K indicated that the saturation magnetic moment in the (Ga_1−xMn_x)N/GaN DFHs decreased with increasing Mn mole fraction and that the saturation magnetic moment and the coercive field in the (Ga_1−xMn_x)N/GaN DFHs were much larger than those in (Ga_1−xMn_x)N thin films. These results indicate that the (Ga_1−xMn_x)N/GaN DFHs hold promise for potential applications in spintronic devices.     

Reentrant spin glass behavior and large initial permeability of Co0.5−xMnxZn0.5Fe2O4

A series of polycrystalline ferrites having nominal chemical composition Co_0.50−xMn_xZn_0.5Fe₂O₄ (0<x<0.4) have been synthesized by the solid-state reaction technique. The XRD analysis confirms single phase cubic spinel structure for all compositions. Lattice constant increases from 0.84195 to 0.84429 nm with the increasing Mn content and obeys Vegard's law. The average grain size increases by increasing both Mn content and sintering temperatures. Room temperature saturation magnetization increases for x=0.1 and decreases for increasing Mn content. The coercivity decreases with increasing Mn content due to the decrease of anisotropy constant. A reentrant spin glass behavior of these samples is observed from the zero field cooled magnetization measurements. The real part of the initial permeability increases by increasing both Mn content and sintering temperatures. This is due to the homogeneous grain growth and densification of the ferrites. The highest initial permeability 137 is observed for x=0.4 sintered at 1573 K on the other hand, the highest relative quality factor (2522) is obtained for the sample Co_0.2Mn_0.3Zn_0.5Fe₂O₄ sintered at 1523 K. The Mn substituted Co_0.50−xMn_xZn_0.5Fe₂O₄ ferrites showed improved magnetic properties.     

Analysis of magnetic field dependent mobility in ferromagnetic Ga1−xMnxAs layers

The magneto-transport properties of ferromagnetic Ga_1−xMn_xAs epilayers with Mn mole fractions in the range of x≈2.2-4.4% were investigated through Hall effect measurements. The magnetic field-dependent Hall mobility for a metallic sample with x≈2.2% in the temperature range of T=0-300 K was analyzed by magnetic field-dependent mobility model including an activation energy of Mn acceptor level. This model provides outstanding fits to the measured data up to T=300 K. It was found that the acceptor levels with activation energies of 112 meV at B=0 Oe decreased to 99 meV at B=5 kOe in the ferromagnetic region. The decrease in acceptor activation energy was due to the spin splitting of the Mn acceptor level in the ferromagnetic region, and was responsible for increase in carrier concentration.     

Ferromagnetism in amorphous Ge1−xMnx grown by low temperature vapor deposition

Magnetic properties of amorphous Ge_1−xMn_x thin films were investigated. The thin films were grown at 373 K on (100) Si wafers by using a thermal evaporator. Growth rate was ∼35 nm/min and average film thickness was around 500 nm. The electrical resistivities of Ge_1−xMn_x thin films are 5.0×10⁻⁴∼100 Ω cm at room temperature and decrease with increasing Mn concentration. Low temperature magnetization characteristics and magnetic hysteresis loops measured at various temperatures show that the amorphous Ge_1−xMn_x thin films are ferromagnetic but the ferromagnetic magnetizations are changing gradually into paramagnetic as increasing temperature. Curie temperature and saturation magnetization vary with Mn concentration. Curie temperature of the deposited films is 80-160 K, and saturation magnetization is 35-100 emu/cc at 5 K. Hall effect measurement at room temperature shows the amorphous Ge_1−xMn_x thin films have p-type carrier and hole densities are in the range from 7×10¹⁷ to 2×10²² cm⁻³.     

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.     

Synthesis and magnetic properties of hexagonal Y(Mn,Cu)O3 multiferroic materials

Single-phase hexagonal-type solid solutions based on the multiferroic YMnO₃ material were synthesized by a modified Pechini process. Copper doping at the B-site (YMn_1−xCu_xO₃; x<0.15) and self-doping at the A-site (Y_1+yMnO₃; y<0.10) successfully maintained the hexagonal structure. Self-doping was limited to y(Y)=2 at% and confirmed that excess yttrium avoids formation of ferromagnetic manganese oxide impurities but creates vacancies at the Mn site. Chemical substitution at the B-site inhibits the geometrical frustration of the Mn³⁺ two-dimensional lattice. The magnetic transition at T_N decreases from 70 K down to 49 K, when x(Cu) goes from 0 to 15 at%. Weak ferromagnetic Mn³⁺-Mn⁴⁺ interactions created by the substitution of Mn³⁺ by Cu²⁺, are visible through the coercive field and spontaneous magnetization but do not modify the overall magnetic frustration. Presence of Mn³⁺-Mn⁴⁺ pairs leads to an increase of the electrical conductivity due to thermally-activated small-polaron hopping mechanisms. Results show that local ferromagnetic interactions can coexist within the frustrated state in the hexagonal polar structure.     

The magnetic map of NiMn alloy thin films on Co(0 0 1) and Co(1 1 1)

Following the experimental work of Groudeva-Zotova et al. [S. Groudeva-Zotova, D. Elefant, R. Kaltofen, D. Tietjen, J. Thomas, V. Hoffmann, C.M. Schneider, J. Magn. Magn. Mater. 263 (2003) 57] where the magnetic and structural characteristics of a bi-layer NiMn-Co exchange biasing systems was investigated, density functional calculations with generalized gradient corrections were performed on (Mn_0.5Ni_0.5)_n ordered alloy on Co(0 0 1) and one Mn_1−xNi_x monolayer on Co(1 1 1). For the Mn_0.5Ni_0.5 monolayer on Co(0 0 1), magnetic moments per surface atom of 0.65 μ_B and 3.76 μ_B were obtained for Ni and Mn, respectively. Those magnetic moments are aligned parallel to the total moment of Co(0 0 1). A complex behavior of the Mn moment in dependence of the thickness “n” is obtained for (Mn_0.5Ni_0.5)_n on Co(0 0 1). Investigations on Mn_1−xNi_x monolayer on Co(1 1 1) have shown that the crystallographic orientation does not modify significantly neither the magnetic moments of Mn and Ni atoms nor their ferromagnetic coupling with the Co(1 1 1) substrate, except for x = 0.66. For x = 0.66 the Mn sub-lattice presents an antiferromagnetic coupling leading to a quenching of the Ni magnetic moment.     

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.     

The structure and luminescence properties of long afterglow phosphor Y3−xMnxAl5−xSixO12

A series of phosphors with the composition Y_3−xMn_xAl_5−xSi_xO₁₂ (x=0, 0.025, 0.050, 0.075, 0.150, 0.225, 0.300) were prepared with solid state reactions. The X-ray powder diffraction analysis of samples shows that the substitution of Mn²⁺ and Si⁴⁺ does not change the garnet structure of phosphors, but makes the interplanar distance decrease to a certain extent. The emission spectra show that Mn²⁺ in Y₃Al₅O₁₂ emits yellow-orange light in a broad band. With the increment of substitution content, the emission intensity of the phosphors increases firstly then decreases subsequently, and the emission peak moves to longer wavelength. Afterglow spectra and decay curves show that all the Mn²⁺ and Si⁴⁺ co-doped samples emit yellow-orange light with long afterglow after the irradiation of ultraviolet light. The longest afterglow time is 18 min. Thermoluminescence measurement shows that there exist two kinds of traps with different depth of energy level and their depth decreases with the increment of substitution content.     

Structural, magnetic and electronic transport properties of MnxGe1−x/Ge(0 0 1) films grown by MBE at 350 °C

We report on the structural, magnetic and electronic transport properties of thin Mn_xGe_1−x films grown at 350 °C. Isolated Mn₅Ge₃ nanoclusters, about 100 nm in size, were formed at the top surface of the film, dominating the magnetic properties of the whole film. Electronic transport properties show Mn doping effect indicating the presence of substitutional Mn ions dispersed in the Ge host, contributing to the formation of a Mn_xGe_1−x diluted phase. Electrical behaviour indicates a saturation effect with the raise of the nominal Mn concentration in the film, above x ≅ 0.03.     

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.