Synthesis and characterization of room-temperature ferromagnetism in Fe- and Ni-co-doped In2O3

Observation of room-temperature ferromagnetism in Fe- and Ni-co-doped In₂O₃ samples (In_0.9Fe_0.1−xNi_x)₂O₃ (0?x?0.1) prepared by citric acid sol-gel auto-igniting method is reported. All of the samples with intermediate x values are ferromagnetic at room-temperature. The highest saturation magnetization (0.453 μ_B/Fe+Ni ions) moment is reached in the sample with x=0.04. The highest solubility of Fe and Ni ions in the In₂O₃ lattice is around 10 and 4 at%, respectively. The 10 at% Fe-doped sample is found to be weakly ferromagnetic, while the 10 at% Ni-doped sample is paramagnetic. Extensive structure including Extended X-ray absorption fine structure (EXAFS), magnetic and magneto-transport including Hall effects studies on the samples indicate the observed ferromagnetism is intrinsic rather than from the secondary impurity phases.     

Nitrogen doping-mediated room-temperature ferromagnetism in insulating Co-doped SnO2 films

Co-doped SnO₂ films codoped with nitrogen (N) have been prepared by magnetron sputtering to investigate the effect of p-type defects on magnetic properties. The incorporation of N modifies the preferential growth orientation of the films. Multiple characterization techniques reveal that the incorporated Co²⁺ and N³⁻ ions substitute for Sn⁴⁺ and O²⁻ sites in SnO₂ lattice, respectively. As N concentration increases, the band gap of the films decreases because of the formation of Sn-N bond. Room-temperature ferromagnetism is observed in (Co, N)-codoped SnO₂ films, and the saturated magnetic moment is sensitive to the incorporated N concentration. The variations in the magnetic properties as a function of N concentration are discussed on the basis of bound magnetic polaron model.     

Effect of thermal treatment in vacuum on Fe-doped SnO2 powders

A sample of 10 at% Fe-doped SnO₂ powder was prepared by mechanical alloying and then thermally treated at 773 K in vacuum. The fit of the diffraction patterns and X-ray absorption spectroscopy measurements revealed that the as milled sample was pure doped rutile. Fe dissolved into SnO₂ was found in Fe²⁺/Fe³⁺ ionic valence with mainly paramagnetic behavior. After the thermal treatment all techniques indicate the formation of the ternary Sn_0.36Fe_2.64O₄ spinel phase, which is responsible for the observed ferromagnetism.     

Study of ferromagnetism in Bi2S3 and ZnS nanocrystalline powders

Results of magnetic measurements suggested that Bi₂S₃ and ZnS nanocrystalline powders prepared by hydrothermal method could possibly exhibit room temperature ferromagnetism. The measured saturation magnetization of the powders increases with an increase of annealing temperature from 300 to 500 °C. Ab initio calculations suggested that the cation vacancies on the surface of Bi₂S₃ and ZnS nanograins could be responsible for the observed magnetic moments. Heat-treatment of Bi₂S₃ or ZnS nanocrystalline powders in Bi or Zn vapor could bring about an enhancement of ferromagnetism. The calculation results indicated that the interstitial Bi or Zn atoms in Bi₂S₃ (0 0 1) or ZnS (0 0 1) surface could induce magnetic moments.     

First-principle study on the electronic and optical properties of Mn-doped SnO2

Using the full-potential linearized augmented plane wave method (FP-LAPW), we have investigated the electronic and optical properties of Sn_1−xMn_xO₂ (x=0, 0.0625, 0.125, 0.1875, 0.25). The doped Mn results in reduction of the band gap, which can be attributed to a series of impurity bands at the bottom of the conduction band caused by the strong hybridization between Mn 3d and O 2p. The results also show that the Mn-doped systems tend to convert into p-type semiconductor with direct band gaps. With the increase of Mn concentration, both the imaginary part of dielectric function and the absorption spectrum show red-shift corresponding to the change of band gaps.     

High coercivity nanocrystalline YCo5 powders produced by mechanical milling

High coercivity nanostructured YCo₅ powders were successfully prepared by mechanical milling of as-cast alloys and subsequent vacuum annealing. Almost single phase YCo₅ alloys, obtained by arc melting, were processed by high energy mechanical milling using a SPEX 8000 mill. After 4 h of milling, powders become nearly amorphous. DSC scans revealed the existence of an irreversible broad exothermic transition with a maximum at 516 °C associated with the crystallization process. Annealing in high vacuum at 800 °C during 2.5 min led to the formation of YCo₅ nanoparticles with an average particle size of 12 nm. A high intrinsic coercivity of 7.23 kOe together with a σ_r/σ_s ratio of 0.75 were obtained.     

Origin of ferromagnetism via hole doping in SnO2: First-principles calculation

First-principles calculations are carried out in order to find the ferromagnetism dependence on the number of holes substituted for Sn sites. The results show that strong localization of defect states of the p bands of the oxygen atoms near the dopants favors high-spin states and local moment formation. These states appear to be ferromagnetically coupled with a rather long-range magnetic interaction, resulting in a half-metallic ferromagnetic ground state for the whole systems. Analysis of the total energies indicates that the induced well-confined ferromagnetism in the oxygen p orbitals due to hole doping is quite possible and easily controlled in these systems, which indicate a new way to develop a half-metallic ferromagnet in nonmagnetic d⁰ oxides.     

Half-metallic ferromagnetism in I2-VI compounds with non-magnetic dopants

First-principles calculations based on the tight-binding linear muffin-tin orbital (TB-LMTO) method were performed to investigate the occurrence of spin polarization in the alkali metal oxides (M₂O) [M: Li, Na, K, Rb] in antifluorite (anti- CaF₂-type) structure with non-magnetic (N, P, As, Sb and Bi) dopants. The calculations reveal that non-magnetic substitutional doping at anion site can induce stable half-metallic ferromagnetic ground state in I₂-VI compounds. Total energy calculations show that the antifluorite ferromagnetic state is energetically more stable than the antifluorite non-magnetic state at equilibrium volume. Ground state properties such as equilibrium lattice constant and bulk modulus were calculated. The calculated magnetic moment is found to be 1.00 μ_B per dopant atom. The magnetic moment is mainly contributed by p orbitals of dopant atom.     

Chemical synthesis of nanocrystalline SnO2 thin films for supercapacitor application

Nanocrystalline SnO₂ thin films were deposited by simple and inexpensive chemical route. The films were characterized for their structural, morphological, wettability and electrochemical properties using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy techniques (SEM), transmission electron microscopy (TEM), contact angle measurement, and cyclic voltammetry techniques. The XRD study revealed the deposited films were nanocrystalline with tetragonal rutile structure of SnO₂. The FT-IR studies confirmed the formation of SnO₂ with the characteristic vibrational mode of Sn-O. The SEM studies showed formation of loosely connected agglomerates with average size of 5-10 nm as observed from TEM studies. The surface wettability showed the hydrophilic nature of SnO₂ thin film (water contact angle 9°). The SnO₂ showed a maximum specific capacitance of 66 F g⁻¹ in 0.5 Na₂SO₄ electrolyte at 10 mV s⁻¹ scan rate.     

Exchange interactions and magnetization reversal of nanocrystalline (NdDyTb)12.3(FeZrNbCu)81.7B6.0 ribbons with Co substitution

Alloys of composition Nd_10.8Dy_0.75Tb_0.75Fe_79.7−xCo_xZr_0.8Nb_0.8Cu_0.4B_6.0 (x=0, 3, 6, 9, 12, 15) were prepared by melt spinning at 22 m/s and subsequent annealing. Phase analysis revealed single-phase materials. Magnetic structure and remanence analysis indicated strong exchange coupling between neighboring grains in all samples. The remanence polarization J_r and maximum energy product (BH)_max increased first and then decreased with further increasing Co content x although the intrinsic coercivity H_ci decreased with increasing x. The increase in remanence polarization J_r by the substitution of Co for Fe is mainly caused by the increase in the saturation polarization J_s rather than by the improvement of exchange-coupling interactions. Optimum magnetic properties with J_r=1.041 T, H_ci=944.9 kA/m and (BH)_max=155.1 kJ/m³ were achieved for x=12 ribbons. The mechanism of magnetic hardening in all samples was of pinning type by analyzing initial magnetization and the dependence on applied magnetizing field of the coercivity and remanence.     

Immiscibility in the Fe3O4-FeCr2O4 spinel binary

A recent thermodynamic model of mixing in spinel binaries, based on changes in cation disordering (x) between tetrahedral and octahedral sites [Am. Mineral. 68 (1983) 18, 69 (1984) 733], is investigated for applicability to the Fe₃O₄-FeCr₂O₄ system under conditions where incomplete mixing occurs. Poor agreement with measured consolute solution temperature and solvus [N. Jb. Miner. Abh. 111 (1969) 184] is attributed to neglect of: (1) ordering of magnetic moments of cations in the tetrahedral sublattice antiparallel to the moments of those in the octahedral sublattice and (2) pair-wise electron hopping between octahedral site Fe³⁺ and Fe²⁺ ions. Disordering free energies (ΔG_D), from which free energies of mixing are calculated, are modeled by

     

Laser fabrication nanocrystalline coatings using simultaneous powders/wire feed

Laser melting deposition (LMD) fabrication is used to investigate feasibilty of simultaneously feeding TC17 wire and the Stellite 20–Si₃N₄–TiC–Sb mixed powders in order to increase the utilization ratio of materials and also quality of LMD composite coatings on the TA1 substrate. SEM images indicated that such LMD coating with metallurgical joint to substrate was formed free of the obvious defects. Lots of the ultrafine nanocrystals (UNs) were produced, which distributed uniformly in some coating matrix location, retarding growth of the ceramics in a certain extent; UNs were intertwined with amorphous, leading the yarn-shape materials to be produced. Compared with substrate, an improvement of wear resistance was achieved for such LMD coating.     

Temperature dependence of electroresistance for La0.67Ba0.33MnO3 manganite

The influence of dc biasing current on temperature dependence of resistance of La_0.67Ba_0.33MnO₃ bulk sample is reported. A decrease in the resistance (electroresistance) on the application of higher bias current is observed. The electroresistance is maximum at metal-insulator transition temperature (T_MI) and decreases when the temperature is either increased or decreased from T_MI. A two-phase model is proposed to explain the occurrence of electroresistance. The higher bias current leads to an increase in alignment of spins and thus, in turn, leads to an increase in spin stiffness coefficient and decrease in the resistance at T_MI.     

A study of room-temperature ferromagnetism in transition metal and fluorine-doped spray-pyrolyzed SnO2 thin films

Room-temperature ferromagnetism has been observed in Co- or Mn-doped SnO₂ and Co- and F-co-doped SnO₂ thin films. A maximum magnetic moment of 0.80μ_B/Co ion has been observed for Sn_0.90Co_0.10O_1.925−δF_0.075 thin films, whereas in the case of Sn_1−xMn_xO_2−δ it was 0.18μ_B/Mn ion for x=0.10. The magnetization of both Sn_1−xCo_xO_2−δ and Sn_1−xCo_xO_2−y−δF_y thin films depends on the free carrier concentration. An anomalous Hall effect has been observed in the case of Co-doped SnO₂ films. However, the same was not observed in the case of Mn-doped SnO₂ thin films. Carrier-mediated interaction is convincingly proved to be the cause of ferromagnetism in the case of Co:SnO₂. It is, however, proposed that no carrier-mediated interaction exists in the case of Mn:SnO₂. Present studies indicate that dopants and hence electronic cloud-lattice interaction plays an important role in inducing ferromagnetism.     

Microstructure and magnetic properties of Fe72.5Cu1M2V2Si13.5B9 (M=Nb, Mo, (NbMo), (MoW)) nanocrystalline alloys

The microstructure and magnetic properties of Finemet-type Fe_72.5Cu₁M₂V₂Si_13.5B₉ (M=Nb, Mo, (NbMo), (MoW)) alloys have been systematically studied. Results show that the nanocrystalline alloy with M=NbMo has the smallest grain size of about 8 nm. The order of the effect of Nb, Mo and W additions in decreasing the α-Fe grain size in nanocrystalline alloys is Nb>Mo>W. The best DC soft magnetic properties are obtained in the alloy with M=Nb. In the case of AC soft magnetic properties, the Nb alloy also exhibits a very low core loss comparing with typical Finemet alloy. Therefore, the Nb alloy is suitable for use as a transformer core material. In addition, it is shown that a narrow grain size distribution and a uniform dispersion of α-Fe grains in the amorphous matrix are very crucial for the development of new Finemet-type nanocrystalline alloys with good soft magnetic properties.     

Nanocrystalline Sr2FeMoO6 prepared by citrate-gel method

Double perovskite Sr₂FeMoO₆ powders with small crystallite size have been synthesised with citrate-gel method. The starting solution pH was varied between 1.5 and 9.0 resulting in large differences in the phase composition and ordering of B^′/B^″ sites. The samples prepared at 975 °C had crystallite sizes under 40 nm whereas crystallite sizes of the samples prepared at 1050 °C were between 78 and 239 nm. The XRD patterns were refined with spacegroup I 4/m, which gave good results for both batches, although clearly better results were obtained with monoclinic P 2₁/n spacegroup for the 975 °C batch. The ordering and the saturation magnetization agreed well with each other after treatment at 1050 °C, but the samples prepared at 975 °C had a strongly reduced saturation magnetization from that given by the ordering.     

Immiscibility in the NiFe2O4-NiCr2O4 spinel binary

The solid solution behavior of the Ni(Fe_1−nCr_n)₂O₄ spinel binary is investigated in the temperature range 400-1200 °C. Non-ideal solution behavior, as exhibited by non-linear changes in lattice parameter with changes in n, is observed in a series of single-phase solids air-cooled from 1200 °C. Air-annealing for 1 year at 600 °C resulted in partial phase separation in a spinel binary having n=0.5. Spinel crystals grown from NiO, Fe₂O₃ and Cr₂O₃ reactants, mixed to give NiCrFeO₄, by Ostwald ripening in a molten salt solvent, exhibited single-phase stability down to about 750 °C (the estimated consolute solution temperature, T_cs). A solvus exists below T_cs. The solvus becomes increasingly asymmetric at lower temperatures and extrapolates to n values of 0.2 and 0.7 at 300 °C. The extrapolated solvus is shown to be consistent with that predicted using a primitive regular solution model in which free energies of mixing are determined entirely from changes in configurational entropy at room temperature.     

Magnetotransport coefficients of Sm0.55Sr0.45MnO3

Measurements of resistivity, magnetization, Seebeck coefficient in 0 and 1.5 T and Nernst coeffecient in 0.3, 0.9 and 1.8 T as a function of temperature on a polycrystalline sample Sm_0.55Sr_0.45MnO₃ are presented. The data demonstrate that an increase in both the carrier density and the mobility of the charge carriers is responsible for the observed colossal magnetoresistance in this compound.     

A simple synthesis and magnetic behavior of nanocrystalline Zn0.9Co0.1O powders by using Zn and Co acetates and polyvinyl pyrrolidone as precursors

This paper reports the synthesis of nanocrystalline powders of Co-doped ZnO (i.e. Zn_0.9Co_0.1O (ZCO)) diluted magnetic semiconductor by a simple method using acetate salts of Zn and Co, and polyvinyl pyrrolidone as precursors. The morphology and crystalline size of the synthesized powders were evaluated by scanning electron microscopy and transmission electron microscopy (TEM). The ZCO powders consist of both nanoparticles with particle sizes of ∼50–100 nm and nanorods with diameters of ∼100–200 and ∼200–500 nm in length. The X-ray diffraction and TEM results indicated that the synthesized ZCO powders had the pure wurtzite structure without any significant change in the structure affected by Co substitution. Optical absorption measurements showed absorption bands indicating the presence of Co ions in substitution of Zn ions. Room-temperature magnetization results revealed a paramagnetic behavior for the ZCO precursor (as grown sample) and a ferromagnetic behavior for the ZCO powders calcined in air at 873 K for 1 h.     

Piezoelectric, dielectric and magnetic properties of (1-x)Pb[Zr, Ti, (Mg1/2W1/2), (Ni1/3Nb2/3)]O3+x(Ni, Co, Cu)FeO4 composites

The phase structure, microstructure, piezoelectric properties, dielectric characteristic and the ME effect of magnetoelectric Pb[Zr_0.23Ti_0.36+0.02(Mg_1/2W_1/2)+0.39(Ni_1/3Nb_2/3)]O₃ (PZT)+xNi_0.8Co_0.1Cu_0.1Fe₂O₄ (NCCF) composite ceramics were prepared by the conventional solid state reaction method. The structural analysis of both the constituent phases and their composites was carried out by X-ray diffraction, energy dispersive spectrometry and scanning electron microscopy. The results showed cubic spinel structure for ferrite phase and tetragonal perovskite structure for ferroelectric phase. The piezoelectric constant, dielectric constant, Curie temperature, remanent polarization and coercive electric field decreased with increase of ferrite content. The coercive field strength, saturation magnetization and remanent magnetization increased with increasing ferrite content.