Mössbauer studies of PbFe2/3W1/3O3 multiferroics

Mössbauer studies of ceramic samples of the antiferromagnetic perovskite PbFe_2/3W_1/3O₃ have been carried out. It has been established that the temperature of transition to the magnetically ordered state is T _N = 365 K. Iron ions in PbFe_2/3W_1/3O₃ are found to reside in the high-spin Fe³⁺ state. The Fe³⁺ ions occupy inequivalent positions differing in the nearest cation environment, or more precisely, tungsten and iron ions are distributed in a random manner over the sites of the octahedral sublattice. The inequivalent positions arise as a result of the Fe and W ions being statistically distributed over the octahedral sublattice. For T > 0 K, magnetic fields at the nuclei and, hence, the average thermodynamic values of the magnetic moments of Fe³⁺ ions occupying inequivalent positions are different and, at a given temperature, are determined by the number of the nearest magnetic neighbors, with the effective magnetic fields (H _eff) varying differently with temperature. As the temperature is lowered, the fields H _eff level off gradually in response to the effective magnetic fields of iron ions having different numbers of exchange bonds leveling off with decreasing temperature which lowers thermal excitation.     

Jahn–Teller effect and superparamagnetism in zn substituted copper-gallate ferrite

Spinel ferrite CuFe₂O₄ and solid solution of Cu_1−xZn_xFe_2−yGa_yO₄ with 0.0?x?0.5 are synthesized through the usual ceramic method. X-ray diffraction measurements confirm the presence of single-phase tetragonal structure with c/a>1for CuFe₂O₄ and compositions with x?0.1. The formation of the tetragonal phase in these samples is attributed to the presence of the cooperative Jahn–Teller Cu ion at the octahedral B-site in the spinel lattice. At the compositional parameter x?0.2, tetragonal-to-cubic transformation occurred and the lattice parameter a for the cubic unit cell is found to decrease with increasing Zn content x. ⁵⁷Fe Mössbauer measurements at 293 K for these compounds reveal superparamagnetic phase for samples with 0.0?x?0.2. In contrast, Mössbauer spectra at 12 K for these materials show well ordered spectra where, the cation distribution and the hyperfine parameters are determined.     

Modifications in magnetic anisotropy of M—type strontium hexaferrite crystals by swift heavy ion irradiation.

Using vibrating sample magnetometery (VSM) 50 MeV Li³⁺ ion irradiation effects on magnetic properties of single crystals of SrGa_xIn_yFe_12−(x+y)O₁₉ (where x=0, 5, 7, 9; y=0, 0.8, 1.3, 1.0), are reported. The substitution of Ga and In in strontium hexaferrite crystals decreases the value of magnetization sharply, which is attributed to shifting of collinear magnetic order to a non-collinear one. Reduction of magnetization is also explained to be as a result of the occupation of the crystallographic sites of Fe³⁺ by Ga³⁺ and In³⁺. The Li³⁺ ion irradiation decreases the value of magnetization, irrespective of whether the crystals are Ga–In substituted or unsubstituted crystals of SrFe₁₂O₁₉. The result is interpreted in terms of the occurrence of a paramagnetic doublet in crystals replacing magnetic sextuplet as a result of irradiation. Substitution of Ga–In in Strontium hexaferrite decreases the value of anisotropy constant. Irradiation with Li³⁺ ions increases the values of anisotropy field for both substituted as well as unsubstituted crystals. Substitution with Ga–In also decreases the Curie temperature (T_c) but the irradiation with Li³⁺ ions does not affect the curie temperature of either Ga–In substituted or pure SrFe₁₂O₁₉ crystals.     

Luminescent and scintillation properties of the Pr3+ doped single crystalline films of Lu3Al5−xGaxO12 garnet

The Pr³⁺ d–f luminescence was investigated in the single crystalline films (SCF) of Lu₃Al_5−xGa_xO₁₂:Pr garnet solid solution at x = 1–3, grown by the liquid phase epitaxy (LPE) method from the melt-solution based on the PbO–B₂O₃ flux. The shape of CL spectra and decay kinetics of Pr³⁺ ions in Lu₃Al_5−xGa_xO₁₂ SCFs strongly depend on the total gallium concentration x and distribution of Ga³⁺ ions between the tetrahedral and octahedral position of the garnet host. The best scintillation properties of Lu₃Al_5−xGa_xO₁₂:Pr SCF are achieved at the nominal Ga content in melt-solution in the x = 2–2.5 range.     

Tailoring of structural, electrical and magnetic properties of BaCo2 W-type hexaferrites by doping with Zr-Mn binary mixtures for useful applications

Single-phase W-type hexaferrite, BaCo₂Fe_16−2x(ZrMn)_xO₂₇ (x=0.0-1.0), has been synthesized by the chemical co-precipitation technique. Mössbauer analysis indicates substitution of Zr ions on tetrahedral (4e and 4f_IV) sites and Mn ions on the octahedral ‘4f_VI site’ at low-doped concentration when the concentration is increased Mn ions but show preference for the octahedral ‘2b site’. The highest enhancement in the value of the room temperature resistivity of 2.82×10⁹ Ω cm has been obtained by doping with Zr-Mn content of x=0.6. The dissipation factor increases from 6.49×10³ to 9.97×10³ at 10 kHz with the addition of Zr-Mn dopants. Such materials are potentially suitable for electromagnetic attenuation purposes, for microwave absorption and as radar absorbing material. High values of saturation magnetization (67 emu/g) and remanent magnetization (34.7 emu/g) are obtained for substitution level of x=0.4 making them suitable for data processing devices.     

Mössbauer investigation of W-type hexaferrite of composition BaZn2−xCoxFe16O27

AbstractPolycrystauine samples of composition BaZn_2–xCo_{x 16}O₂₇ (O2-W undergoes a transition from planar to conical order at 515±5 K.     

Neutron diffraction and Mössbauer study on FeGa x Cr2−x S4

Ga doped sulphur spinel FeGa _x Cr_2?x S₄ (x = 0.1 and 0.3) have been studied with X-ray, neutron diffraction, and Mössbauer spectroscopy. Rietveld refinement of X-ray, neutron diffraction, and Mössbauer spectroscopy lead to the conclusion that the samples are in inverse spinel type, where most Ga ions are present at octahedral site (B). The neutron diffractions on FeGa _x Cr_2?x S₄ (x = 0.1) above 10 K show long range interaction behaviors and reveal a ferrimagnetic ordering, with the magnetic moment of Fe²⁺(?3.45 μ_B) aligned antiparallel to Cr³⁺ (+2.89 μ_B) at 10 K. Fe ions migrate from the tetrahedral (A) site to the octahedral (B) site with an increase in Ga substitutions. The electric quadrupole splittings of the A and B sites in Mössbauer spectra give direct evidence that Ga ions stimulate an asymmetric charge distribution of Fe ions in the A site.     

Synthesis and electrical conductivity of various melilite-type electrolytes Ln1 + xSr1 − xGa3O7 + x/2

Melilite type ceramics ABC₃O₇ such as La_1.54Sr_0.46Ga₃O_7.27 are a new class of oxide conductors where the conductivity is carried out through interstitial oxygen ions. This work presents the attempt to replace the A-site element La with the other lanthanide elements and Y, resulting in various Ln_1 + xSr_1 − xGa₃O_7 + x/2 ceramics, in which Ln = La, Pr, Nd, Sm, Eu, Gd, Dy, Yb, Y, and 0.1 < x < 0.54. X-ray diffraction analysis shows that the melilite structure could be formed when the replacement is conducted with most lanthanides but not Yb and Y. Impedance spectroscopy demonstrates that the conductivity decreases dramatically with the decreasing of Ln³⁺ size and the charge-carrier concentration. These results suggest that, as an interstitial oxide ion electrolyte, La_1.54Sr_0.46Ga₃O_7.27 is the most promising ceramic in the Ln_1 + xSr_1 − xGa₃O_7+x/2 melilite family since La³⁺ has the largest ionic radius of the lanthanide elements.     

Synthesis and magnetic properties of La-substituted M-type Sr hexaferrites

Single-phase M-type hexagonal ferrites Sr_1−xLa_xFe₁₂O₁₉ (0≤x≤1) were prepared by a ceramic route. The stability limits of the ferrite phases were determined with a combination of various microscopy techniques, electron-probe micro-analysis, powder X-ray diffraction and thermal analysis. SrFe₁₂O₁₉ (x=0) is stable up to 1420 °C, whereas LaFe₁₂O₁₉ (x=1) exists between 1360 and 1400 °C only. The lattice parameters of Sr_1−xLa_xFe₁₂O₁₉ exhibit a linear variation with x, i.e. a₀ slightly increases and c₀ decreases with x, leading to a decrease of the unit cell volume with x. The saturation magnetization at T=5 K decreases with increasing La concentration. Room temperature Mössbauer analysis shows that the Fe³⁺/Fe²⁺ valence change occurs in the 2a sites for the whole composition range.     

BaAl12O19:Mn green emitting nanophosphor for PDP application synthesized by solution combustion method and its Vacuum Ultra-Violet Photoluminescence Characteristics

Nanostructured BaAl₁₂O₁₉:Mn²⁺ phosphor particles of nano-rod morphology with diameter 40-100 nm and length up to 200-600 nm has been synthesized by solution combustion method and its photoluminescence characteristics have been studied by Vacuum Ultra-Violet Photoluminescence spectrometer (VUVPL) under 147 nm excitation. The crystallographic phase purity of BaAl₁₂O₁₉:Mn²⁺ nanostructured phosphor particle synthesized by solution combustion approach is confirmed by X-ray diffraction (XRD). The broadening of XRD diffraction peaks indicates nanocrystalline nature of particles present in powder. The emission spectrum of BaAl₁₂O₁₉:Mn²⁺ nanophosphor on 147 nm excitation consists of a wide green band with a peak at about 515 nm, which is due to a 3d⁵ (⁴T_1g)-3d⁵ (⁶A_1g) transition corresponds of Mn²⁺ ions. It is found that the concentration quenching is obtained when Mn²⁺ content (x) is 0.05 in BaAl₁₂O₁₉:xMn²⁺ nanophosphor on 147 nm excitation. The decay time of 3d⁵ (⁴T_1 g)-3d⁵ (⁶A_1 g) transition of Mn²⁺ ions at 147 nm excitation is about 23 ms for BaAl₁₂O₁₉:Mn²⁺ nanophosphor. This nanostructured green emitting BaAl₁₂O₁₉:Mn²⁺ phosphor can find potential application in Plasma Display Panels (PDPs) and mercury-free fluorescent lamps.     

Spectral studies on Cr ions doped in sodium-lead borophosphate glasses

Electron paramagnetic resonance (EPR), optical absorption and emission spectra of Cr³⁺ ions doped in (30−x) (NaPO₃)₆+30PbO+40B₂O₃+xCr₂O₃ (x=0.5, 2.0, 3.0, 4.0 and 5.0 mol%) glasses have been studied. The EPR spectra exhibit resonance signals with effective g values at g≈4.55 and g≈1.97. The EPR spectra of x=3.0 mol% of Cr₂O₃ in sodium-lead borophosphate glass sample were studied at various temperatures (295-123 K). The intensity of the resonance signals increases with decrease in temperature. The optical absorption spectrum exhibits four bands characteristic of Cr³⁺ ions in octahedral symmetry. From the analysis of the bands, the crystal-field parameter Dq and the Racah interelectronic repulsion parameters B and C have been evaluated. The emission spectrum exhibit one broad band characteristic of Cr³⁺ ions in octahedral symmetry. This band has been assigned to the transition ⁴T_2g (F)→⁴A_2g (F). Correlating EPR and optical data, the molecular bonding coefficient (α) has been evaluated.     

Fabrication and hard X-ray photoemission analysis of photocathodes with sharp solar-blind sensitivity using AlGaN films grown on Si substrates

Photocathode devices operating in reflection-mode, where the photoemission is detected on the same side as the light irradiation, were developed for the detection of deep ultraviolet light by using p-Al_xGa_1−xN films grown on Si(1 1 1) substrates. The external quantum efficiencies were as high as 20-15% at 200 nm and 280 nm, while the value was as low as 10⁻²% at 310 nm. The on-off ratio was more than four orders of magnitude, which represents high solar-blind sensitivity. The escape probability of Al_xGa_1−xN photocathode was decreased with increase of AlN mole fraction. The effective barrier potential against the photoelectron emission near the surface was reduced due to the upward shift of conduction band of Al_xGa_1−xN. The photoemission from the Al_xGa_1−xN films terminated with Cs-O adatoms will be discussed in terms of band diagrams that were evaluated by hard X-ray photoelectron spectroscopy.     

Jahn-Teller transition in Al doped LiMn2O4 spinel

Al-doped lithium manganese spinels, with starting composition Li_1.02Al_xMn_1.98−xO₄ (0.00<x≤0.06), are investigated to determine the influence of the Al³⁺ doping on the Jahn-Teller (J-T) cooperative transition temperature T_J-T. X-ray powder diffraction (XRPD), nuclear magnetic resonance, electron paramagnetic resonance, conductivity and magnetic susceptibility data are put into relation with the tetrahedral and octahedral occupancy fraction of the spinel sites and with the homogeneous distribution of the Al³⁺ ions in the spinel phase. It is observed that Al³⁺ may distribute between the two cationic sublattices. The J-T distortion, associated with a drop of conductivity near room temperature in the undoped sample, is shifted towards lower temperature by very low substitution. However, for x>0.04 T_J-T it increases with increasing x, as clearly evidenced in low temperature XRPD observations. A charge distribution model in the cationic sublattice, for Al substitution, is proposed to explain this peculiar behavior.     

Effect of WO3 on EPR, structure and electrical conductivity of vanadyl doped WO3·M2O·B2O3 (M=Li, Na) glasses

Glasses with composition xWO₃·(30−x)M₂O·70B₂O₃ (M=Li, Na; 0≤x≤15) doped with 2 mol% V₂O₅ have been prepared using the melt-quench technique. The electron paramagnetic resonance spectra have been recorded in X-band (ν≈9.14 GHz) at room temperature (RT). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) only due to V⁴⁺ ions, which exist as VO²⁺ ions in octahedral coordination with a tetragonal compression in the present glass system. The tetragonality increases with WO₃:M₂O ratio and also there is an expansion of 3d_xy orbit of unpaired electron in the vanadium ion. The study of IR transmission spectra over a range 400-4000 cm⁻¹ depicts the presence of WO₆ group. The DC conductivity (σ) has been measured in the temperature range 423-623 K and is found to be predominantly ionic.     

Magnetic ordering in Ni–Cd ferrite

A series of Ni_1−xCd_xFe₂O₄ (0.0≤x≤0.8) were prepared by conventional double sintering ceramic method and sintered at 1200 °C for 6 h. X-ray diffraction results confirmed the single-phase spinel structures of all the samples. The Curie temperature decreases linearly with increasing Cd content, which is explained due to the weakening of the A–B exchange interaction. The sample with x=0.7 shows re-entrant type of spin glass phase transitions. The magnetic moment and saturation magnetization at 20 K are found to increase with Cd content up to x=0.5 and then tends to decrease for x>0.5. The increase in magnetic moment with cadmium is attributed to Neel's two sublattice (A- and B-sublattice) collinear models according to which the magnetic moment is the vector sum of the lattice magnetic moment. The decrease in magnetization for x>0.5 obeys the Yafet–Kittel (Y–K) model. The increase in Y–K angles for x>0.3 indicates the increased tendency for triangular spin arrangements on B-sites. This suggests the existence of a canted spin structure in the ferrite system with higher content of Cd.     

Synthesis,structure and magnetic properties of layered manganate Sr4Mn3−xCrxO10 (x=0, 0.2)

The manganates Sr₄Mn_3−xCr_xO₁₀ (x=0 and 0.2) have been synthesized by solid state reaction. Powder X-ray diffraction analysis shows orthorhombic symmetry with space group Cmca for both compounds. The magnetic susceptibility measurements show an antiferromagnetic transition at 192 and 176 K for x=0 and 0.2, respectively. The magnetic susceptibility data were estimated using a model based on spin exchange antiferromagnetic interactions in isolated (Mn⁴⁺) trimer; a paramagnetic contribution due to the chromium ions was added in the case of Cr-doped materials.     

Structure,analysis and some magnetic properties for low temperature fired Ni–Cu ferrite

Cu²⁺ ions substituted Ni-ferrite having the general formula Ni_1-xCu_xFe₂O₄ (where x=0.0, 0.2, 0.4 and 0.6) were prepared by the sintering ceramic method. X-ray diffraction, infrared spectra and magnetization of the above ferrite were carried out to investigate structural and magnetic characterization of this ferrite. Crystallite size, lattice parameters, positional oxygen parameter and ionic radii for both tetrahedral and octahedral sites were calculated. The experimental lattice parameter was found to vary between 8.3856 and 8.3865 Å. The infrared spectra were measured in the frequency range 650–150 cm⁻¹. Two prominent bands were observed, high frequency band ν₁ and low frequency band ν₂ were assigned to tetrahedral and octahedral sites. Bond length and force constant were also calculated for both tetrahedral and octahedral sites. The effect of Cu concentration on, saturation magnetization, coercivity ratio and magnetic moment were investigated using vibrating sample magnetometer (VSM). It was found that both saturation magnetization (M_S) and coercivity (H_c) decreases with increasing in Cu content.     

A Mössbauer spectroscopy and neutron diffraction study of magnetostrictive,melt-spun Fe–Ga alloy ribbons

Ribbons of Fe_100−xGa_x (x=15, 17.5, 19.5 and 22.5) were prepared by rapid solidification from the melt. ⁵⁷Fe Mössbauer spectroscopy and high resolution neutron diffraction have revealed that Fe_100−xGa_x alloys with x=15 and 17.5 have the disordered bcc (A2) structure even after annealing, but the alloy with x=19.5 developed the short-range ordered D0₃ phase when annealed. The x=22.5 alloys showed mainly D0₃ phase with a fraction of bcc phase. A fraction of the bcc phase transformed into D0₃ phase and the long-range ordering of D0₃ phase was improved after annealing. ⁵⁷Fe Mössbauer spectra showed no observable L1₂ phase in any samples even though less than 1% volume of L1₂ phases has been found in the annealed samples by neutron diffraction. The additional absorption at hyperfine field of 25 T in x=22.5 samples was regarded as a result of imperfect D0₃ structure, rather than L1₂ phase.     

The temperature evolution of the magnetic correlations in pure and diluted spin ice Ho2−xYxTi2O7

Diffuse polarized neutron scattering studies have been carried out on single crystals of pyrochlore spin ice Ho_2−xY_xTi₂O₇ (x=0, 0.3, and 1) to investigate the effects of doping and anisotropy on spin correlations in the system. The crystals were aligned with the (1 −1 0) orientation coincident with the direction of neutron polarization. For all the samples studied the spin flip (SF) diffuse scattering (i.e. the in-plane component) reveals that the spin correlations can be described using a nearest-neighbour spin ice model (NNSM) at higher temperatures (T=3.6 K) and a dipolar spin ice model (DSM) as the temperature is reduced (T=30 mK). In the non-spin flip (NSF) channel (i.e. the out-of-plane component), the signature of strong antiferromagnetic correlations is observed for all the samples at the same temperature as the dipolar spin ice behaviour appears in the SF channel. Our studies show that the non-magnetic dopant Y does not significantly alter SF or NSF scattering for the spin ice state, even when Y doping is as high as 50%. In this paper, we focus on the experimental results of the highly doped spin ice HoYTi₂O₇ and compare our results with pure spin ice Ho₂Ti₂O₇. The crossover from a dipolar to a nearest-neighbour spin ice behaviour and the doping insensitivity in spin ices are briefly discussed.     

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.