Magnetic properties of doped ZnO prepared by different synthetic routes

We have studied the magnetic properties of Zn_0.96M_0.04O (M=Mn, Fe, Co) compounds prepared using several routes. The low temperature ceramic synthesis gave multiphasic samples and show ferromagnetic behavior. Single phases can be obtained by heating at higher temperatures (∼900–1100 °C). The use of very low oxygen pressure also favours the preparation of single-phases. We were also successful in preparing single-phase samples at very low temperature (∼400 °C) by using a sol-gel method. All of the samples without noticeable secondary phases in the X-ray patterns behave as conventional paramagnets. This is true even for the samples with very low grain size. Samples exhibiting secondary phases reveal spontaneous magnetization even at room temperature in some cases. Our results strongly support that ferromagnetism at room temperature is always due to the presence of secondary phases and not to the doping of ZnO.     

Extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) study of melt-spun Fe85Ga15 ribbons

The local structure in melt-spun Fe₈₅Ga₁₅ ribbons with a width ∼3 mm and thickness ∼60 μm produced in argon atmosphere was studied by analyzing EXAFS and XANES data. The following results were obtained: Ga–Ga bonds were not detected excluding the tendency to form clusters of Ga atoms; Ga substitutes Fe creating a local strain of about +1% on the first shell Fe–Ga bond, whereas on the second Fe–Ga shell strain quickly relaxes down to +0.3%; XANES spectra are compatible with a random substitution of Fe atoms by Ga atoms in the A2 structure. From the AFM investigation, we observed that at the surface (free side) of the ribbon the particles are elongated along the ribbon (∼2 μm×∼5 μm) and each particle is formed by small grains of average size of 200 nm.     

Synthesis and magnetic properties of Ni-doped zinc oxide powders

Polycrystalline Zn_1−xNi_xO diluted magnetic semiconductors have been successfully synthesized by an auto-combustion method. X-ray diffraction measurements indicated that the 5 at% Ni-doped ZnO had the pure wurtzite structure. Refinements of cell parameters from powder diffraction data revealed that the cell parameters of Zn_0.95Ni_0.05O were a little bit larger than ZnO. Transmission electron microscopy observation showed that the as-synthesized powders were of the size ∼60 nm. Magnetic investigations showed that the nanocystalline Zn_0.95Ni_0.05O possessed room temperature ferromagnetism with the saturation magnetic moment of 0.1 emu/g (0.29 μ_B/Ni²⁺).     

Effect of size and synthesis route on the magnetic properties of chemically prepared nanosize ZnFe2O4

Magnetization of the ZnFe₂O₄ sample of average size 4 nm measured with SQUID in the temperature range 5–300 K shows anomalous behaviour in field cooled (FC) and zero-field-cooled (ZFC) conditions. The FC and ZFC curves measured in 50 Oe field cross each other a little before the peaks. No such anomaly is observed with samples of 6 nm particle size made with the same procedure. The characteristics of the FC and ZFC curves are very different in ZnFe₂O₄ samples of the same size (6 nm) made via two different chemical routes. The genesis of these differences are suggested to be in cationic configuration and spin disorder. Fe-extended X-ray absorption fine structure (EXAFS) studies show that there is around 80% inversion in case of zinc ferrite (ZnFe₂O₄) with the particle size 4 nm, whereas ZnFe₂O₄ of size 6 nm shows 40% inversion. The samples with an average particle size of 7 nm and more show negligible inversion. Theoretical simulations suggest that the electrostatic energy of the system plays a crucial role in deciding the cationic configuration of spinel ferrites.     

ZnO-Fe3O4 composite prepared by sol-gel method with H2 deoxidation

Fe doped ZnO powder samples (Fe/Zn=0.05 and 0.1) were prepared by sol-gel method with H₂ deoxidation at 450 ^°C for several hours or just heated in air at the same temperature. It was showed by vibrating sample magnetometer (VSM) that samples heat treated in H₂ could show strong ferromagnetism at room temperature while samples treated in air only show very weak magnetism. XRD using Co kα X-ray revealed that the samples heated in H₂ were not pure phase but like a granular system and the magnetism mainly results from Fe₃O₄ in samples while samples heated in air showed pure ZnO phase. Our work indicated that H₂ deoxidation treatment may be an effective technique to fabricate such magnetic semiconductor-like materials with Curie temperature higher than room temperature.     

Growth and characterization of rocksalt MnS/GaAs epilayers by hot-wall epitaxy

Epitaxial growth characteristics of α-MnS on GaAs(1 0 0) substrates have been investigated by X-ray diffraction and double crystal rocking curve measurements. Growth of stoichiometric α-MnS films has been performed by hot-wall epitaxy using Mn and ZnS as a source of sulfur. The films on GaAs(1 0 0) at low substrate temperature exhibit multiphase crystal structures of zincblende and rocksalt, and the main structure is changed to rocksalt with increasing substrate temperature. Photoluminescence spectrum of the α-MnS epilayer at 5 K exhibits broad emission bands, which are attributed to Mn²⁺ ions. The band gap energy of the α-MnS epilayer at room temperature was also estimated to be about 3.3 eV by reflection.     

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.     

Synthesis and magnetic characterization of nickel ferrite nanoparticles prepared by co-precipitation route

Magnetic nanoparticles of nickel ferrite (NiFe₂O₄) have been synthesized by co-precipitation route using stable ferric and nickel salts with sodium hydroxide as the precipitating agent and oleic acid as the surfactant. X-ray diffraction (XRD) and transmission electron microscope (TEM) analyses confirmed the formation of single-phase nickel ferrite nanoparticles in the range 8-28 nm depending upon the annealing temperature of the samples during the synthesis. The size of the particles (d) was observed to be increasing linearly with annealing temperature of the sample while the coercivity with particle size goes through a maximum, peaking at ∼11 nm and then decreases for larger particles. Typical blocking effects were observed below ∼225 K for all the prepared samples. The superparamagnetic blocking temperature (T_B) was found to be increasing with increasing particle size that has been attributed to the increased effective anisotropy energy of the nanoparticles. The saturation moment of all the samples was found much below the bulk value of nickel ferrite that has been attributed to the disordered surface spins or dead/inert layer in these nanoparticles.     

Phase transition and extended X-ray absorption fine structure of melt-spun amorphous Fe100−xYx alloys

The phase diagram and local structure of melt-spun amorphous (a-) Fe_100−xY_x (22?x?62) alloys were investigated using AC and DC magnetic and extended X-ray absorption fine structure (EXAFS) measurements. The a-Fe–Y system shows reentrant spin glass (RSG) behavior for 42?x?58 and spin glass (SG) behavior for 60?x. Two SG transition temperatures, T_g and T_f, were obtained in the RSG state. The T_g, T_f and Curie temperature T_C decrease with increasing x, and the T_C and T_g vanish at x=60. A new magnetic phase diagram for the melt-spun a-Fe_100−xY_x alloys was obtained from magnetic measurements for higher Y concentration. The magnetic states of the a-Fe_100−xY_x alloys change remarkably around x=60 and an EXAFS study revealed that the average atomic distance between nearest-neighboring Fe atoms changes at approximately x=60.     

Investigating the formation and magnetic properties of the Dy0.75Fe1.25O3 orthoferrite prepared by sol-gel method

In this paper, the Dy_0.75Fe_1.25O₃ orthoferrite nanoparticles were synthesized successfully by sol-gel method. Dy_0.75Fe_1.25O₃ orthoferrite nanoparticles are obtained by calcining the flakes at 600 and 700 °C. The magnetic properties of the different samples are investigated using Quantum Design MPMS SQUID magnetometer and MS-500 Mössbauer spectrometer. Magnetic phase γ-Fe₂O₃ coexists in the samples calcined at 600 °C and orthoferrite phase is completely recovered in the samples calcined at 700 °C. Although excessive Fe³⁺ ions were introduced, none of these iron spins couple magnetically with Dy³⁺ ions.     

Synthesis and properties of magnetic fluid based on iron nanoparticles prepared by a vapor-phase condensation process

Magnetic fluid containing metallic iron nanoparticles was successfully fabricated in this work. The iron nanoparticles were synthesized by chemical vapor condensation process and then dispersed in water-base solution (pH 11) with oleic acid as surfactant. More than 80% of iron nanoparticles were fully dispersed in the fluid and remained stable without any further oxidation over 200 h. Both the iron nanoparticles and the subsequent magnetic fluid exhibited typical ferromagnetic behavior.     

The magnetic properties of Be-codoped GaMnN grown via molecular beam epitaxy

GaMnN and Be-codoped GaMnN were grown via molecular beam epitaxy using a single GaN precursor and their structural and magnetic properties were examined. X-ray diffraction and superconducting quantum interference device (SQUID) measurements revealed that the grown layers are homogeneous without precipitates. The saturation magnetization of GaMnN has increased from ∼4 to ∼16 emu/cm³ via codoping of Be. The d–d exchange interaction between Mn atoms was discussed for the ferromagnetism of GaMnN.     

Influence of annealing temperature on structural, optical and magnetic properties of Mn-doped ZnO thin films prepared by sol-gel method

Thin films of Zn_1−xMn_xO (x=0.01) diluted magnetic semiconductor were prepared on Si (1 0 0) substrates by the sol-gel method. The influence of annealing temperature on the structural, optical and magnetic properties was studied by X-ray diffraction (XRD), atom force microscopy (AFM), photoluminescence (PL) and SQUID magnetometer (MPMS, Quantum Design). The XRD spectrum shows that all the films are single crystalline with (0 0 2) preferential orientation along c-axis, indicating there are not any secondary phases. The atomic force microscopy images show the surfaces morphologies change greatly with an increase in annealing temperature. PL spectra reveal that the films marginally shift the near band-edge (NBE) position due to stress. The magnetic measurements of the films using SQUID clearly indicate the room temperature ferromagnetic behavior, and the Curie temperature of the samples is above room temperature. X-ray photoelectron spectroscopy (XPS) patterns suggest that Mn²⁺ ions were successfully incorporated into the lattice position of Zn²⁺ ions in ZnO host. It is also found that the post-annealing treatment can affect the ferromagnetic behavior of the films effectively.     

Adsorption model determination of N2O/Ag(1 1 0) by theoretical studies of near-edge X-ray absorption fine structure

The nitrogen 1s near-edge X-ray absorption fine structure (NEXAFS) spectra of the N₂O adsorbed on Ag(1 1 0) have been studied by the multiple-scattering cluster (MSC) and self-consistent field (SCF) DV-Xα methods. Two adsorption models, in which the N₂O molecule attached to the Ag substrate through the central nitrogen (N_C) atom and the terminal nitrogen (N_T) atom, respectively, have been checked up thoroughly. The MSC calculation and the R-factor analysis show that the N₂O molecule is attached to the Ag substrate through the terminal nitrogen atom with the adsorption height h = 3.4 ± 0.1 Å. In the overlayer the N₂O molecules arrange themselves into a tilted chain due to the interaction between the cations and the anions in the molecules. The physical cause of the resonances in the NEXAFS spectra mentioned above has been discussed by the DV-Xα method, which confirms the MSC calculations.     

Synthesis and magnetic properties of Zn1−xMnxO films prepared by the sol-gel method

We report on the ferromagnetic characteristics of Zn_1−xMn_xO films (x=0.1-0.3) prepared by the sol-gel method on silicon substrates using transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), X-ray diffractometry (XRD) and superconducting quantum interference device (SQUID) magnetometry at various temperatures. Magnetic measurement show that the Curie temperature (T_C) and the coercive field (H_C) were ∼39 K and ∼2100 Oe for the film of x=0.2, respectively. EDS and TEM measurements indicate that Mn content at the interface is significantly higher than that at the center of the Zn_0.8Mn_0.2O film showing the ratio, Zn:Mn:O≅1:12:15. This experimental evidence suggests that ferromagnetic precipitates containing manganese oxide may be responsible for the observed ferromagnetic behavior of the film.     

Effect of anions on the phase stability of γ-FeOOH nanoparticles and the magnetic properties of gamma-ferric oxide derived from lepidocrocite

The effect of anions such as Cl⁻, SO₄²⁻, and HPO₄²⁻ on the phase stability of FeOOH (α or γ) during precipitation is investigated. Oxidation of Fe(OH)₂·xH₂O from FeCl₂ solution with high Cl⁻ concentration ([Cl⁻]/[Fe]=R_Cl≥8) or (NH₄)₂Fe(SO₄)₂ (FAS) with [HPO₄²⁻]/[Fe]=R_P≥0.02 yields phase-pure γ-FeOOH. In the medium ranges of R_Cl and R_P, mixed phases of α-FeOOH and γ-FeOOH are obtained. Replacement of OH⁻ by Cl⁻ with the bridging cations or strongly bonded HPO₄²⁻ ions in the matrix of the intermediate phase (Fe_x²⁺Fe_y³⁺(OH)_2x+2y−nz·xH₂O(A)_zⁿ⁻, where A is anions such as Cl⁻, SO₄²⁻, HPO₄²⁻, etc.), promoted the lower density γ-FeOOH. However, the particles are less developed and have poor crystallinity as evidenced from transmission electron microscope and thermogravimetry-differential thermal analysis of the precipitates. Whereas, monophasic, uniformly sized, nano-lath shaped particles with high aspect ratio >10 are obtained when morphology-controlling cation additives such as Pt⁴⁺, Pd²⁺ or Rh³⁺ are present in FeCl₂ (R_Cl≥8) solution. Preferential adsorption of additives on (0k0) and (h00) planes limits the growth in the perpendicular directions leading to high aspect ratios. The effect of these additives are suppressed by the phosphate ion, a strong complexing ligand, giving rise to fibrous aggregate with the length of individual particles as small as 10-30 nm. While most of the Cl⁻ ion is removed from the final precipitates on washing, phosphate remained as HPO₄²⁻ as evidenced from IR absorption spectra. Maghemite obtained by dehydroxylating γ-FeOOH contains randomly distributed micropores bringing in the relaxation effects of spins on the surface atoms as deciphered from Mössbauer spectroscopy. This leads to the low σ_s (44-48 emu/g) and H_c (120-130 Oe) for γ-Fe₂O_3−δ particles. Whereas nearly pore-free single crystalline particles obtained by reduction followed by reoxidation has high value of σ_s (73 emu/g) and H_c (320 Oe), which decreases to 30 emu/g and 75 Oe, respectively, for nanoparticles obtained from phosphate stabilized lepidocrocite. The mobility of iron ions and counter mobility of vacancies during the topotactic transformation of γ-FeOOH to magnetite to γ-Fe₂O_3−δ renders the particles pore-free.     

Microcharacterization of the surface oxidation of Py/Cu multilayers by scanning X-ray absorption spectromicroscopy

The local surface oxidation of the permalloy surface layer in Py/Cu GMR multilayers on a micron lateral scale has been analyzed by means of a microspot-X-ray absorption spectromicroscope utilizing synchrotron radiation from the Advanced Light Source bending magnet beamline 6.3.2. Additionally, the GMR multilayer samples prepared by dc magnetron sputtering have been analyzed by cross-sectional transmission electron microscopy, hard X-ray reflection and magnetoresistance measurements. The formation of a passivating iron-oxide layer on the sample surface was identified by X-ray absorption near edge structure spectroscopy (XANES) near the Fe-2p edge while no indication for nickel-oxide formation could be found. Small micron-size pits of reduced iron-oxide concentration could be identified by XANES microscopy while the corresponding nickel distribution appeared to be homogeneous. The results are explained in terms of a local breakdown of the passivating oxide layer. Received:16 October 2000 / Accepted: 4 December 2000 / Published online: 21 March 2001     

Discussion again of the magnetic and transport property of Ag-doped LaMnO3

Samples La_1−aAg_aMnO₃ (0.05?a?0.50) were sol–gel fabricated. A part of Ag was found to dissociate and run off the samples in sintering process when sintering temperature exceeds 700 °C, resulting in a composite of La_1−xAg_xMnO₃ and MnO₂/Mn₂O₃. The magnetic and transport properties of the composite have been studied. The sample with the nominal composition La_0.7Ag_0.3MnO₃ was found to show the greatest magnetoresistance in the sample group. Detailed analysis on average Mn valence reveals a composite of (La_0.985Ag_0.015MnO₃)_0.776[(MnO₂)_0.590(Mn₂O₃)_0.410]_0.224. Its MR ratio at room temperature exceeds 24% under a field of 1.8 T. A conductivity leap has been observed around a=0.30. It suggests a kind of field-induced fluctuation in percolation in the samples investigated.     

Electronic structure of CeAl2 thin films studied by X-ray absorption spectroscopy

We report X-ray absorption near edge structures (XANES) study of CeAl₂ thin films of various thicknesses, 40-120 nm, at Al K- and Ce L₃-edges. The threshold of the absorption features at the Al K-edge shifts to the higher photon energy side as film thickness decreases, implying a decreased in Al p-orbital charges. On the other hand, from Ce L₃-edge spectra, we observed a decrease in the 5d4f occupancy as the surface-to-bulk ratio increases. The valence of Ce in these thin films, as revealed by the Ce L₃-edge spectral results, is mainly trivalent. From a more detailed analysis we found a small amount of Ce⁴⁺ contribution, which increases with decreasing film thickness. Our results indicate that the surface-to-bulk ratio is the key factor which affects the electronic structure of CeAl₂ thin films. The above observations also suggest that charge transfer from Al to Ce is associated with the decrease of the film thickness.     

Nanoparticle chain-like formation in electrical double-layered magnetic fluids evidenced by small-angle X-ray scattering

Small-angle X-ray scattering (SAXS) was performed on a series of Electric Double-Layered Magnetic Fluids (EDL-MF) composed of ferrite type-- CoFe₂O₄, MnFe₂O₄, ZnFe₂O₄, NiFe₂O₄ and CuFe₂O₄--nanoparticles of different crystalline sizes ( D _XR ranging from 40 to 139?, as determined by X-ray diffraction). The information concerning the scattering objects was obtained through the analysis of the distance distribution function p(r) and of the size distribution function D(R), both retrieved from SAXS data. The results show that EDL-MF, in the absence of an applied magnetic field, are composed of small magnetic particle aggregates in solution. These agglomerates are elongated in one direction (chain-like) with the longest dimension varying from 240 to 330?. The cross-section size is of the order of D _XR. The data also demonstrate that the maximum dimension of these aggregates is independent of the ferrite type. On the other hand, the number of aggregated magnetic particles is nanoparticle-size-dependent. Accordingly, larger ferrite-type nanoparticles as those with D _XR = 139? form aggregates composed of 2-3 magnetic particles, whereas smaller ones with D _XR 40? form agglomerates of about 6 magnetic particles in solution. As the nanoparticle size is reduced, it might increase the particle surface defects. Such occurrence would affect the particle surface charge density, which could reduce the electrostatic screening, favoring the agglomeration phenomenon. Received 28 February 2000 and Received in final form 28 August 2000