Phonon dynamics of hexagonal Y Mn1−xFexO3

Phonon dynamics was investigated on Y Mn_1−xFe_xO₃(0≤x≤0.20) hexagonal manganite polycrystals. Phonon modes were properly assigned using results obtained on Y MnO₃ single crystal, by mixing the ab plane and the c axis optical responses. Upon increasing the Fe content, most of the phonon mode frequencies do not vary drastically. However, some modes involving Y and O atom displacements along the c axis are affected by doping. Indeed, a redshift of their transverse optical frequency was interpreted as an elongation of Y-O distance along the c-axis, resulting in a change in yttrium coordination.     

Photoluminescence properties of Sr1-xSi2O2N2: Eux as green to yellow-emitting phosphor for blue pumped white LEDs

This study evaluated potential applications of green to yellow-emitting phosphors (Sr_1−xSi₂O₂N₂: Eu²⁺_x) in blue pumped white light emitting diodes. Sr_1-xSi₂O₂N₂: Eu²⁺_x was synthesized at different Eu²⁺ doping concentrations at 1450 °C for 5 h under a reducing nitrogen atmosphere containing 5% H₂ using a conventional solid reaction method. The X-ray diffraction patterns of the prepared phosphor (Sr_1-xSi₂O₂N₂: Eu²⁺_x) were indexed to the SrSi₂O₂N₂ phase and an unknown intermediate phase. The photoluminescence properties of these phosphors (Sr_1−xSi₂O₂N₂: Eu²⁺_x) showed that the samples were excited from the UV to visible region due to the strong crystal field splitting of the Eu²⁺ ion. The emission spectra under excitation of 450 nm showed a bright color at 545-561 nm. The emission intensity increased gradually with increasing Eu²⁺ doping concentration ratio from 0.05 to 0.15. However, the emission intensity decreased suddenly when the Eu²⁺ concentration ratio was >0.2. As the doping concentration of Eu²⁺ was increased, there was a red shift in the continuous emission peak. These results suggest that Sr_1-xSi₂O₂N₂: Eu₂⁺_x phosphor can be used in blue-pumped white light emitting diodes.     

Some studies about the green and red light emitting structures in NaCl1−xBrx:Mn

In this work we present the results obtained from the luminescence spectra and X-ray diffraction as well as transmission electron microscopy, at room temperature on crystals of NaCl_1−xNaBr_x:MnCl₂:0.3% (x=0.00, 0.05, 0.25, and 0.50). The results suggest the existence of structures between the crystal planes (1 1 1) and (2 0 0), which may be associated with different types of Mn²⁺ arrangements, such as dipole complexes, octahedral and rhombohedral structures as well as other possible nanostructures that include mixtures of bromine/chlorine ions. These are responsible for the emission spectra of “as grown” crystals consisting of maxima around 500 nm and 600 nm. The green emission has been usually attributed to rhombohedral/tetrahedral symmetry sites; the present results point out that this is due to Mn–Cl/Br nanostructures with rhombohedral structure. On the other hand when the crystals are thermally quenched from 500 °C to room temperature the structures previously detected present changes. Only a red band appears around 620 nm if the samples are later annealed at 80 °C.     

Growth and properties of magnetron cosputtering grown MnxGe1−x on Si (001)

We have grown Mn_xGe_1−x films (x=0, 0.06, 0.1) on Si (001) substrates by magnetron cosputtering, and have explored the resulting structural, morphological, electrical and magnetic properties. X-ray diffraction results show there is no secondary phase except Ge in the Mn_0.06Ge_0.94 film while new phase appears in the Mn_0.1Ge_0.9 film. Nanocrystals are formed in the Mn_0.06Ge_0.94 film, determined by field-emission scanning electron microscopy. Hall measurement indicates that the Mn_0.06Ge_0.94 film is p-type semiconductor and hole carrier concentration is 6.07×10¹⁹ cm⁻³ while the Mn_xGe_1−x films with x=0 has n-type carriers. The field dependence of magnetization was measured using alternating gradient magnetometer, and it has been indicated that the Mn_0.06Ge_0.94 film is ferromagnetic at room temperature.     

Highly cation-deficient manganese perovskite, La1−xMn1−yO3 with x=y

Oxidative (δ>0) nonstoichiometry in the perovskite ‘LaMnO_3+δ’ has been known to be manifested not with O interstitials but rather with cation vacancies of equal amounts at the two cation sites, La and Mn, i.e. La_1−xMn_1−yO₃ with x=y. Here, we report the fabrication of samples with record-high cation-vacancy concentrations (x>0.12 or δ>0.4) by means of a variety of high-pressure oxygenation techniques. Linear (negative) dependence of the cell volume on x was observed within the whole x range investigated, down to 56.9 Å³ (per formula unit) for a sample oxygenated at 5 GPa and 1100 °C using Ag₂O₂ as an excess oxygen source. With increasing degree of cation deficiency in La_1−xMn_1−xO₃, the ferromagnetic transition temperature was found to follow a bell shape with respect to x exhibiting a maximum of ∼250 K about x≈0.1. For moderately oxygenated samples large magnetoresistance effect was evidenced.     

Effect of In ions doping on the structural and magnetic properties of Mg0.2Mn0.5Ni0.3InxFe2−xO4 spinel ferrites

Effect of substitution of diamagnetic trivalent indium ions on the composition Mg_0.2Mn_0.5Ni_0.3In_xFe_2−xO₄ with x varying from 0.1 to 0.3 in steps of 0.1 using citrate precursor techniques has been investigated. Single-phase cubic spinel structure of these samples has been confirmed from X-ray diffraction analyses. Micro structural features were examined by TEM images. Lattice constant ‘a’ initially increases up to x = 0.1 and thereafter it decreases with further increase in x. This indicates that variation of ‘a’ with x do not obey Vegard's law. Nonlinear behavior of ‘a’ with x may be due to substitutional effect of larger In³⁺ ions (0.91Å) with smaller Fe³⁺ ions (0.67Å) in Mg-Mn-Ni ferrite. Ferrites have been investigated for their structural and magnetic properties such as variations in lattice constant, saturation magnetization, coercivity, retentivity, initial permeability, magnetic loss and relative loss factor (RLF). Fairly constant value of initial permeability over a wide frequency range (0.075–10 MHz) and low values of relative loss factor of order of 10⁻⁶–10⁻⁵ in same frequency range are main achievement of present investigations. RLF has been reduced by three orders of magnitude as compared to those samples prepared by conventional method. Low values of relative loss factor even at a high frequency indicate that prepared materials may have great potential for use in microwave devices. Possible mechanisms contributing to these properties have been discussed in this paper.     

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.     

Magnetic phase diagram of double-layered La2−2xCa1+2xMn2O7 manganite

Double-layered manganite La_2−2xCa_1+2xMn₂O₇ have been synthesized for compositions ‘x’=0.0, 0.1, 0.2, 0.3, 0.4 and 0.5 by solid state reaction method. From X-ray diffraction study, their crystal structures were found to be tetragonal perovskite with lattice parameters decreasing with increasing ‘x’. The decreasing lattice parameters affect the balance between in-plane, intra-bilayer and inter-bilayer exchange interactions, which is reflected on magnetotransport properties. The metal-to-insulator transition temperature is found to vary with composition and peaked around ‘x’=0.3. From ac-susceptibility study, 2D-ferromagnetic ordering was observed at higher temperatures for all compositions whereas 3D-ferromagnetic ordering was observed at quite low temperatures. In low-temperature region, decreasing susceptibility shows antiferromagnetic state for all compositions. On the basis of electrical and magnetic properties, a magnetic phase diagram is given.     

Li0.5Fe2.5−xMnxO4 ferrite sintered from microwave-induced combustion

Li_0.5Fe_2.5−xMn_xO₄ (0≦x≦1.0) powders with small and uniformly sized particles were successfully synthesized by microwave-induced combustion, using lithium nitrate, ferric nitrate, manganese nitrate and carbohydrazide as the starting materials. The process takes only a few minutes to obtain as-received Mn-substituted lithium ferrite powders. The resultant powders annealed at 650 ^°C for 2 h and were investigated by thermogravimeter/differential thermal analyzer (TG/DTA), X-ray diffractometer (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), and thermomagnetic analysis (TMA). The results revealed that the Mn content were strongly influenced the magnetic properties and Curie temperature of Mn-substituted lithium ferrite powder. As for sintered Li_0.5Fe_2.5−xMn_xO₄ specimens, substituting an appropriate amount of Mn for Fe in the Li_0.5Fe_2.5−xMn_xO₄ specimens markedly improved the complex permeability and loss tangent.     

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.     

Band-edge exciton transitions in (Ga1−xMnx)N diluted magnetic semiconductor films with above room temperature ferromagnetic transition

(Ga_1−xMn_x)N thin films grown on GaN buffer layers by using molecular beam epitaxy were investigated with the goal of producing diluted magnetic semiconductors (DMSs) with band-edge exciton transitions for applications in optomagnetic devices. The magnetization curve as a function of the magnetic field at 5 K indicated that ferromagnetism existed in the (Ga_1−xMn_x)N thin films, and the magnetization curve as a function of the temperature showed that the ferromagnetic transition temperature of the (Ga_1−xMn_x)N thin film was above room temperature. Photoluminescence and photoluminescence excitation spectra showed that band-edge exciton transitions in (Ga_1−xMn_x)N thin films appeared. These results indicate that the (Ga_1−xMn_x)N DMSs with a magnetic single phase hold promise for potential applications in spin optoelectronic devices in the blue region of the spectrum.     

Preparation, crystal structure and photoluminescence of Mn-doped magnesium pyroborates solid solutions, (Mg1-xMnx)2B2O5

Solid solutions of manganese(II)-doped magnesium pyroborate, ((Mg_1−xMn_x)₂B₂O₅, 0<x≤0.30, triclinic system, space group: P1¯ (no. 2)), were synthesized by solid state reaction. The unit cell parameters were refined by the Rietveld method of powder X-ray diffraction patterns. (Mg_1−xMn_x)₂B₂O₅ showed broad red emission at 670 nm under 414 nm excitation. The wavelengths of the emission peak did not depend on the manganese content. Absorption of the d-d transitions of Mn²⁺ ions was observed in the photoluminescence excitation spectra. The emission intensity reached the maximum at a Mn content (x) of 0.05 and decreased with increasing x from 0.05 to 0.30.     

Substitutional sites of Co ions in CuGa1−xAlxSe2:Co crystals

The substitutional sites of Co²⁺ ions in Co²⁺-doped CuG_1−xAl_xSe₂ (including CuGaSe₂ where x=0 and CuAlSe₂ where x=1) semiconductors are studied by analyzing the composition x dependence of optical spectral parameters reported in the previous literature for these materials. From the studies, we suggest that Co²⁺ occupy I-group cation site rather than III-group cation site. The suggestion is discussed.     

Formation mechanism of ferromagnetism in Si1−xMnx diluted magnetic semiconductors

Si_1−xMn_x diluted magnetic semiconductor (DMS) bulks were formed by using an implantation and annealing method. Energy dispersive X-ray fluorescence, transmission electron microscopy (TEM), and double-crystal rocking X-ray diffraction (DCRXD) measurements showed that the grown materials were Si_1−xMn_x crystalline bulks. Hall effect measurements showed that annealed Si_1−xMn_x bulks were p-type semiconductors. The magnetization curve as a function of the magnetic field clearly showed that the ferromagnetism in the annealed Si_1−xMn_x bulks originated from the interaction between interstitial and substitutional Mn⁺ ions, which was confirmed by the DCRXD measurements. The magnetization curve as a function of the temperature showed that the ferromagnetic transition temperature was approximately 75 K. The present results can help to improve understanding of the formation mechanism of ferromagnetism in Si_1−xMn_x DMS bulks.     

Superconductivity in CoSr2(Y1−xCax)Cu2O7+δ

The roles of aliovalent Ca^II-for-Y^III substitution and high-pressure-oxygen annealing in the process of ‘superconducterizing’ the Co-based layered copper oxide, CoSr₂(Y_1−xCa_x)Cu₂O_7+δ (Co-1212), were investigated. The as-air-synthesized samples up to x=0.4 were found essentially oxygen stoichiometric (−0.03≤δ≤0.00). These samples, however, were not superconducting, suggesting that the holes created by the divalent-for-trivalent cation substitution are trapped on Co in the charge reservoir. Ultra-high-pressure heat treatment carried out at 5 GPa and 500 °C for 30 min in the presence of Ag₂O₂ as an excess oxygen source induced bulk superconductivity in these samples. The highest T_c was obtained for the high-oxygen-pressure treated x=0.3 sample at ∼40 K.     

Optical properties and deep levels in annealed Si1−xMnx bulk materials

The optical properties and the deep levels in bulk Si_1−xMn_x formed by using an implantation and annealing method were investigated. Transmission electron microscopy, X-ray diffraction, and Hall-effect measurements showed that the annealed bulk Si_1−xMn_x samples were p-type crystalline semiconductors. The photoluminescence spectra for the annealed bulk Si_1−xMn_x material showed luminescence peaks corresponding to excitons bound to neutral acceptors and related to dislocations due to the existence of Mn impurities. Deep-level transient spectroscopy results for the annealed bulk Si_1−xMn_x showed deep levels related to the interstitial and substitutial sites of the Mn⁺ ions. These results can help improve understanding of the optical properties and the deep levels in annealed bulk Si_1−xMn_x material.     

Effect of Mn-site vacancies on the magnetic entropy change and the Curie temperature of La0.67Ca0.33Mn1−xO3 perovskite

Single-phase polycrystalline samples of La_0.67Ca_0.33Mn_1−xO₃ (x=0.00, 0.02, 0.04, 0.06) have been prepared using the sol-gel method. The structure, magnetocaloric properties and the Curie temperature of the samples with different Mn vacancy concentrations have been investigated. The experimental results show that vacancy doping at the Mn-sites has a significant influence on the magnetic properties of La_0.67Ca_0.33Mn_1−xO₃. The Curie temperature decreases monotonically with increasing the Mn-site vacancy concentration x. A remarkable enhancement of the magnetic entropy change has been obtained in the La_0.67Ca_0.33Mn_0.98O₃ sample. The entropy change reaches |ΔS_M|=3.10 J kg⁻¹ K⁻¹ at its Curie temperature (264 K) under an applied magnetic field H=10 kOe, which is almost the same value as that of pure Gd.     

Structural and photoluminescence properties of thermally evaporated Cd1−xMnxS nano-crystalline films

Thin films of Cd_1−xMn_xS (0≤x≤0.5) were formed on glass substrates by resistive vacuum thermal evaporation. All the films were deposited at 300 K and the films were annealed at 373, 473 and 573 K for 1 h in a vacuum of 10⁻⁶ mbar. Atomic force microscopy (AFM) studies showed that all the films investigated were in nano-crystalline form with a grain size in the range 36-82 nm. All the films exhibited a wurtzite structure of the host material. The lattice parameters varied linearly with composition following Vegard’s law in the entire composition range. Photoluminescence studies showed that two distinct emission bands were observed for each Cd_1−xMn_xS compound. One corresponds to internal transition and the other one is due to the transition of Mn²⁺ ions in interstitial sites or in small ‘Mn’ chalcogenic clusters.     

Structural and magnetic phase diagram and room temperature CMR effect of La1−xAgxMnO3

The study of the structural and magnetic phase diagram of the manganites La_1−xAg_xMnO₃ shows similarity with the La_1−x′Sr_x′MnO₃ series, involving a metallic ferromagnetic domain at relatively high temperature (≈300 K). The Ag-system differs from the Sr-one by a much smaller homogeneity range (x≤1/6) and the absence of charge ordering. But the most important feature of the Ag-manganites deals with the exceptionally high magnetoresistance (−25%) at room temperature under 1.2 T, that appears for the composition x=1/6. The latter is interpreted as the coincidence of the optimal double exchange condition (Mn³⁺:Mn⁴⁺=2) with T_max=300 K (maximum of the ρ(T) curve in zero field).