Room temperature ferromagnetism in Fe-doped CeO2 thin films grown on LaAlO3 (001)

Ce_1 − xFe_xO_2 − δ/LaAlO₃(001) thin films (x = 0.01 and 0.03) have been prepared by pulsed laser deposition method and thoroughly characterized using X-ray diffraction (XRD), dc magnetization, near edge X-ray absorption fine structure (NEXAFS), and X-ray magnetic circular dichroism (XMCD). XRD data reveal a single-phase cubic structure with a strong crystallographic orientation along the (200) plane. Room temperature ferromagnetism is confirmed through isothermal hysteresis as well as temperature dependent magnetization measurements, which clearly show the ferromagnetic Curie temperature occurring at least above 350 K. The Fe L_3,2 edge NEXAFS spectra for both Fe-doped thin films exhibit mixed valent Fe²⁺/Fe³⁺ states, whereas Ce M_5,4 edge shows the 4+ state of Ce, throughout the doping. With the increase in Fe doping, Fe²⁺ state increases and a simultaneous decrease in magnetization value is also observed. The XMCD signal of both samples reveals the ferromagnetic ordering of substituted Fe ions in the ceria matrix. Our results indicate that ferromagnetism is intrinsic to the ceria system and is not due to any secondary magnetic impurity.     

Magnetization and crystal structure of RF-sputtered nanocrystalline CuFe2O4 thin films

Cu-ferrite films were deposited on glass substrates by RF-magnetron sputtering in pure Ar and mixture of (Ar + O₂) environment. The XRD studies of the as-deposited films indicate nanocrystalline cubic spinel structure. The observed increase in the intensity of (400) line at the expense of (220) line with increase in O₂ content is ascribed to the change in distribution of Cu and Fe-ions among tetrahedral A-site and octahedral B-sites. The highest saturation magnetization (M_S) of 264 emu/cm³ (in-plane) and 188 emu/cm³ (out of-plane) was obtained for the as-deposited films in pure Ar. The high deposition rate in reducing atmosphere leads to the formation of Cu⁺ ions which prefer occupation of the A-site in the spinel structure displacing Fe³⁺ cations to occupy the B-sites giving rise to the change in cation distribution among A and B-sites and consequently leading to high value of M_S. The decrease in M_S value with increase in oxygen content is ascribed to the decrease in film growth rate and Cu⁺ concentration which allow the cations to take up their preferable sites. The observed change in the film properties with environment is due to the presence of multivalent copper and iron ions with differing site preferences.     

Influence of preparation condition and doping concentration of Fe-doped ZnO thin films: Oxygen-vacancy related room temperature ferromagnetism

Fe-doped and Fe-Ga co-doped ZnO diluted magnetic semiconductor thin films on quartz substrate were studied. Rapid annealing enhanced the ferromagnetism (FM) of the films grown in Ar/O₂. All the films grown in Ar are n-type and the carrier concentration could increase significantly when Ga is doped. The state of Fe in the films was investigated exhibiting Fe³⁺. Magnetic measurements revealed that room temperature ferromagnetism in the films were doping concentration dependent and would enhance slightly with Ga doping. The origin of the observed FM is interpreted by the overlapping of polarons mediated through oxygen vacancy based on the bound magnetic polaron model.     

Characteristics of NixFe100−x films deposited on SiO2/Si(1 0 0) by DC magnetron co-sputtering

Ni_xFe_100−x films with a thickness of about 200 nm were deposited on SiO₂/Si(1 0 0) substrates at room temperature by DC magnetron co-sputtering using both Fe and Ni₈₀Fe₂₀ targets. Compositional, structural, electrical and magnetic properties of the films were investigated. Ni₇₆Fe₂₄, Ni₆₅Fe₃₅, Ni₆₀Fe₄₀, Ni₅₅Fe₄₅, Ni₄₉Fe₅₁ films are obtained by increasing the sputtering power of the Fe target. All the films have a fcc structure. Ni₇₆Fe₂₄, Ni₆₅Fe₃₅, Ni₆₀Fe₄₀ and Ni₅₅Fe₄₅ films grow with crystalline orientations of [1 1 1] and [2 2 0] in the direction of the film growth while the Ni₄₉Fe₅₁ film has the [1 1 1] texture structure in the direction of the film growth. The lattice constant of the film increases linearly with increasing Fe content. All of the films grow with thin columnar grains and have void networks in the grain boundaries. The grain size does not change markedly with the composition of the film. The resistivity of the film increases with increasing Fe content and is one order of magnitude larger than that of the bulk. For all the films the magnetic hysteresis loop shows a hard magnetization. The Ni₇₆Fe₂₄ film has the lowest saturation magnetization of 6.75×10⁻² T and the lowest saturation field of 8.36×10⁴ A/m while the Ni₄₉Fe₅₁ film has a largest saturation magnetization of 9.25×10⁻² T and the largest saturation field of 1.43×10⁵ A/m.     

Ce and oxygen vacancy mediated tuning of structural and optical properties of CeO2 nanoparticles

Ceria nanoparticles were synthesized by hydrolysis of cerium nitrate in basic medium. The cubic fluorite structure of ceria was confirmed by XRD. From TEM studies ceria nanoparticles were found to be spherical in shape with an average diameter of 5 nm. The prepared nanoparticles have a predominant orientation along (2 2 2) crystallographic plane. Oxygen vacancies and Ce³⁺ lead to the lattice expansion and strain in CeO₂. Peak asymmetry and broadening of Raman active mode peak further confirms the presence of these defects. Total concentration of oxygen vacancies that are present in the ceria nanocrystallites is calculated to be 1.234 × 10²⁰ cm⁻³. These oxygen vacancies and ceria related defects result in an effective red shifting of the band gap by changing its structural regularity. The visible luminescence peaks are also caused by these Ce³⁺ and oxygen vacancy centers.     

Correlation between resistivity and oxygen vacancy of hydrogen-doped indium tin oxide thin films

Thin films of indium tin oxide (ITO) sputter-deposited by dc-plasma containing deuterium on glass substrate without any heat treatments exhibited gradual lowering in electrical resistivity with increasing the deuterium content [D₂] in plasma gas by 1% and then demonstrated a jump in resistivity by further increase of [D₂] than 1%. X-ray photoelectron spectroscopy revealed that hydroxyl-bonded oxygen in ITO grew continuingly with [D₂]. Deuterium positioned at the interstitial site increased almost quantitatively with increasing [D₂]. Rutherford backscattering spectroscopy showed gradual reduction in the oxygen content of ITO with increasing [D₂] by 1% and then demonstrated an abrupt increase of the oxygen content with the increase of [D₂] than 1%. The films with [D₂] < 1% were oxygen deficient, but those with [D₂] > 1% were excess of oxygen. The most oxygen deficient film of [D₂] = 1% was the most conductive. Behavior in the resistivity with [D₂] looks parallel to that in the oxygen content. A lower resistivity of the films corresponded well to oxygen vacancy rather than hydrogen interstitial.     

Effect of background gas environment on oxygen incorporation in TiN films deposited using UHV reactive magnetron sputtering

The effect of the base pressure on the incorporation of oxygen into reactively magnetron-sputtered metal-nitride films has been investigated. A UHV sputtering system with a base pressure of less than 10⁻⁶ Pa was used to examine the relationship between a deliberately introduced background pressure of oxygen and a measured oxygen content in the sputter-deposited TiN films. The results showed that with an oxygen partial pressure of 10⁻⁴ Pa, the deposited TiN was found to include 10-20 at.% of oxygen when measured by the technique of X-ray photoelectron spectroscopy (XPS). When no oxygen was admitted into the system, no trace of oxygen could be detected in the deposited TiN films. The incorporation mechanism is discussed in terms of the coverage-dependent sticking probabilities of O₂ and N₂ on a Ti metal surface.     

Effect of oxygen flow rate on ITO thin films deposited by facing targets sputtering

Tin-doped indium oxide (ITO) thin films were deposited on glass substrates at various oxygen flow rates using a planar magnetron sputtering system with facing targets. In this system, the strong internal magnets inside the target holders confine the plasma between the targets. High resolution transmission electron microscopy revealed a combination of amorphous and crystalline phases on the glass substrate. X-ray photoelectron spectroscopy suggested that the decrease in carrier concentration and increase in mobility were caused by a decrease in the concentration of Sn⁴⁺ states. The electrical and optical properties of the ITO films were examined by Hall measurements and UV-visible spectroscopy, which showed a film resistivity and transmittance of 4.26 × l0⁻⁴ Ω cm, and > 80% in the visible region, respectively.     

Cu2O thin films deposited by reactive direct current magnetron sputtering

The Cu₂O thin films were prepared on quartz substrate by reactive direct current magnetron sputtering. The influences of oxygen partial pressure and gas flow rate on the structures and properties of deposited films were investigated. Varying oxygen partial pressure leads to the synthesis of Cu₂O, Cu₄O₃ and CuO with different microstructures. At a constant oxygen partial pressure of 6.6 × 10^− 2 Pa, the single Cu₂O films can be obtained when the gas flow rate is below 80 sccm. The as-deposited Cu₂O thin films have a very high absorption in the visible region resulting in the visible-light induced photocatalytic activity.     

Low temperature luminescence of KMgF3:Eu crystal

Paper presents luminescence spectra and time resolved spectra of KMgF₃:Eu²⁺ system obtained at different temperatures and pressures, under excitation with 325 nm. At temperatures between 200 K and 292 K the spectra consist of sharp line peaked at 27,830 cm⁻¹ related to ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺ accompanied by the phonon sideband. Under pressure the red spectral shift with the rate equal to −0.6 cm⁻¹/kbar is observed. Luminescence decay is single-exponential with the lifetime equal to 5.2 ms independent of pressure and temperature. The emission spectra obtained at temperatures lower than 125 K consist of 5 sharp lines peaked at 27,590 cm⁻¹, and 27,670 cm⁻¹, 27,722 cm⁻¹, 27,766 cm⁻¹ and 27,809 cm⁻¹, that relative intensity depends on temperature. Pressure shift of these lines was found to be equal to −0.6 cm⁻¹/kbar; the same as ⁶P_7/2 → ⁸S_7/2 transition in Eu²⁺, whereas their lifetime is shorter and is equal to 0.7 ms at 100 K. These new lines disappear at temperature greater than 200 K. We tentatively related them to the luminescence of Eu²⁺-F center (fluorine vacancy with electron) complex.     

Studies on the structure and gas sensing properties of nickel–cobalt ferrite thin films prepared by spin coating

The influence of Co²⁺ ions content on structure and sensing properties of Ni_1−xCo_xFe₂O₄ (x = 0.25, 0.5, 0.75) thin films deposited on glass substrates by spin coating is presented. Structural characterization evidenced thin films with cubic spinel structures and morphologies dependent on cobalt content. Repartition of cations in spinel tetrahedral and octahedral sites was determined and was found that the presence of Co²⁺ ions in octahedral sites favor the formation of Fe²⁺ species. The sensitivity to some reducing vapor gases (acetone, liquefied petroleum gas LPG, ethyl alcohol and methyl alcohol) was investigated and was found that thin films with x = 0.75 exhibit high sensitivity to ethyl alcohol and thin films with x = 0.25 have high sensitivity to acetone. This sensitivity largely depends on the temperature and test gas concentration and was related to the Fe²⁺ species formed in octahedral sites.     

Significant improvement of the oxygen permeation flux of tubular Ba0.5Sr0.5Co0.8Fe0.2O3 − δ membranes covered by a thin La0.6Sr0.4Ti0.3Fe0.7O3 − δ layer

We present a new method to improve the oxygen flux properties and stability of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ tube membrane using a thin layer of La_0.6Sr_0.4Ti_0.3Fe_0.7O_3 − δ as protective coatings. The first relevant result is that the La_0.6Sr_0.4Ti_0.3Fe_0.7O_3 − δ protective layer had an extraordinary positive effect on improving the oxygen permeation flux of the tubular Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ membranes. La_0.6Sr_0.4Ti_0.3Fe_0.7O_3 − δ-coated Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ tubular membrane showed the highest oxygen permeability with the flux reaching ~ 3 ml cm⁻² min⁻¹ (oxygen purity > 99%) at 950 °C in static atmospheric pressure through a 1.0 mm thick membrane.     

Effect of oxygen partial pressure on the microstructural and physical properties on nanocrystalline tin oxide films grown by plasma oxidation after thermal deposition from pure Sn targets

In this work, microstructural and physical properties were studied in the tin oxide films deposited by thermal evaporation of Sn films on stainless steel substrates followed by in situ D.C. plasma oxidation at 200 °C substrate temperature. The surface properties were studied by scanning electron microscopy, X-ray diffraction, atomic force microscopy and four-point probe electrical resistivity. The typical calculated grain size of the films deposited by thermal evaporation was between 28 nm and 66 nm and the texture structure was found to be dependent on the thermal deposition pressure. A cassiterite structure of SnO₂ was produced by D.C. plasma oxidation with the main diffraction peaks of the (101), (200), (211), (310) and (221) planes at the 25% and 50% O₂ partial pressure conditions. However, at 12.5% O₂ partial pressure oxidation conditions, amorphous tin oxide structure and crystalline SnO phases were detected. Increasing thermal deposition pressure resulted in preferential texture formation at (211) and (310) planes. The surface structure investigation of the produced films by SEM and AFM studies showed large SnO₂ islands with approximately 1.0 μm and 1.5 μm sized nodules, and they are called as grape-like structures. The grape-like grains possess nano grains, which are between 20 nm and 30 nm in diameter calculated by Scherer's formula. The grape-like grains were seen to be separated by large cavities and the size of these cavities and nano grains was seen to be larger when the O₂ partial pressure is increased. The four-point probe resistivity of the films, grown at different oxidation temperatures, decreased with the increase in oxygen partial pressure. The values of resistivity for SnO₂ phase were measured as low as 10⁻⁵ Ω-cm and observed to decrease with increasing thermal deposition pressure and oxygen partial pressure.     

Intrinsic room temperature ferromagnetism in Zn0.92Co0.08O thin films prepared by pulsed laser deposition

Zn_0.92Co_0.08O thin films were fabricated on p-type Si (100) and quartz substrates by pulsed laser deposition using a ZnCoO ceramic target. The structural and magnetic properties of the films were characterized by field emission scan electronic microscopy, x-ray diffraction, x-ray photoemission spectroscopy, UV-visible transmission spectra, extended x-ray absorption fine structure spectroscopy and physical property measurement system. Substitutional doping of Co²⁺ in ZnO lattice is demonstrated in the films. The as-deposited Zn_0.92Co_0.08O thin film displayed intrinsic room temperature ferromagnetism with saturation magnetization (M_s) of ~ 0.20μ_B/Co. The corresponding M_s increased to ~ 0.23μ_B/Co when annealed in vacuum and further to ~ 0.42μ_B/Co after annealed in hydrogen. In turn, the M_s dropped to the value of ~ 0.13μ_B/Co after annealed in oxygen. Our studies indicate that oxygen vacancy density plays a key role in mediating the ferromagnetism of the diluted magnetic semiconductor films.     

AC conductivity, density related and magnetic properties of Ni1 − xZnxFe2O4 ferrites with the variation of zinc concentration

AC conductivity, density related and magnetic properties are reported for Ni_1 − xZn_xFe₂O₄ ferrites with the variation of zinc concentration prepared by the standard solid state reaction technique. X-ray powder diffraction patterns confirmed the spinel structure of the prepared compounds. AC conductivity (lnσ_ac) increases from − 10.045 (S/m) to − 3.781 (S/m) with the increase in zinc concentration from 0.0 to 1.0 at the frequency of 1 kHz. Lattice parameters, sintered density and grain size increase whereas X-ray density and porosity decrease with the increase in zinc concentration. Saturation magnetization increases with the increase in zinc concentration up to x = 0.4 and after that it decreases with the increase in zinc concentration. Remanence magnetization and magnetic moment almost have the similar trend as that of saturation magnetization. Yafet-Kittel angles increase with the increase in zinc concentration. The possible reasons responsible for these changes are undertaken.     

Magnetic properties of nano-clusters lanthanum chromite powders doped with samarium and strontium ions synthesized via a novel combustion method

A novel approach to synthesize a single-phase orthorhombic perovskite lanthanum chromite LaCrO₃ clusters doped with Sm³⁺ and Sr²⁺ ions via gel combustion route was reported. The producing materials were synthesized using metal nitrates as oxidizers and triethanol amine (TEA), N-butyl amine (NBA) or ethylene diamine (EDA) as a fuel. The effect of the annealing temperature, type of organic fuel and the variation of the samarium and/or strontium substitution and its impact on crystal structure, crystallite size, microstructure and magnetic properties of the LaCrO₃ powders formed was systematically studied. The results revealed that a well crystalline single phase of pure LaCrO₃ can be achieved at annealing temperature from 800 to 1000 °C for 2 h. Moreover, each organic carrier materials exhibited a different degree of effectiveness in the synthesis of the mixed oxide powders. The crystal structure was influenced by doped Sm³⁺ and/or Sr²⁺ ions. The crystallite size of the produced powders was increased with the increase the annealing temperature, increasing the Sm³⁺ ion and the decrease of Sr²⁺ ion substitution. The microstructures of the produced powders were found to be nanoclusters octahedra-like shaped. The saturation magnetization of the LaCrO₃ powders increased continuously with an increase in the Sm³⁺ ion concentration and it decreased with an increase in the Sr²⁺ ion up to 0.3 at annealing temperature of 1000 °C for 2 h. The maximum saturation magnetization (0.279 emu/g) was achieved at the Sm³⁺ ion molar ratio 0.3 and annealing temperature 1000 °C. Moreover, wide coercivities can be obtained at different synthesis conditions (49.25 to 522  Oe).     

Physicochemical properties of solid-solid interactions in nanosized NiO-substituted Fe2O3/TiO2 system at 1200 °C

The solid-solid interactions between nanosized pure and NiO-substituted ferric and titanium(IV) oxides have been investigated using XRD technique and microstructure studies, also magnetic properties were studied using vibrating samples magnetometer (VSM). The amounts of substituting Ni²⁺ were x = 0, 0.2, 0.4, 0.6, 0.8 and 1 mole. A mixture equimolar proportions of finely powdered Fe₂O₃ and TiO₂ were mixed with NiO, ball milled, compressed at 250 kg/cm² and fired at 1200 °C for 4 h.The obtained results showed that with substituting Ni²⁺ concentration x = 0 only Fe₂TiO₅ phase is present (∼80 nm) which showed a very small saturation magnetic flux density (B_s), remnant magnetic flux density (B_r) and the maximum energy product (BH)_max. By the addition of x = 0.2 NiO, new phases were observed NiTiO₃ and NiFe₂O₄ of crystallite sizes 160 and 110 nm, respectively. By the increase of substituting Ni²⁺ concentration the NiTiO₃ and NiFe₂O₄ phases increased on the expense of Fe₂TiO₅ up to x = 0.4, then the increase in substituting Ni²⁺ concentration led to a decrease in Fe₂TiO₅ and NiTiO₃ while NiFe₂O₄ increases which results in a great improvement of magnetic properties.All samples exhibit a catalytic activity towards H₂O₂ decomposition and the values of rate constant increase with increasing amount of Ni²⁺ substituting. The most acidic active sites are shown by specimens substituted with x = 0 this concludes that H₂O₂ decomposition is not favored on acidic active sites.     

Structure and magnetic property of CoFe2−xSmxO4 (x = 0–0.2) nanofibers prepared by sol–gel route

CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers with diameters about 100–300 nm have been prepared using the organic gel-thermal decomposition method. The composition, structure and magnetic properties of the CoFe_2−xSm_xO₄ nanofibers were investigated by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, inductive coupling plasma mass analyzer and vibrating sample magnetometer. The CoFe_2−xSm_xO₄ (x = 0–0.2) nanofibers obtained at 500–700 °C are of a single spinel structure. But, at 800 °C with a relatively high Sm content of 0.15–0.2 the spinel CoFe_2−xSm_xO₄ ferrite is unstable and the second phase of perovskite SmFeO₃ occurs. The crystalline grain sizes of the CoFe_2−xSm_xO₄ nanofibers decrease with Sm contents, while increase with the calcination temperature. This grain reduction effect of the Sm³⁺ ions doping is largely owing to the lattice strain and stress induced by the substitution of Fe³⁺ ions with larger Sm³⁺ ions in the ferrite. The saturation magnetization and coercivity increase with the crystallite size in the range of 8.8–57.3 nm, while decrease with the Sm content from 0 to 0.2 owing to a smaller magnetic moment of Sm³⁺ ions. The perovskite SmFeO₃ in the composite nanofibers may contribute to a high coercivity due to the interface pinning, lattice distortion and stress in the ferrite grain boundary fixing and hindering the domain wall motion.     

Soft magnetic and high-frequency properties of Ni-Zn ferrite film with FeMn underlayer

Ni_0.45Zn_0.55Fe₂O₄ (40 nm) single-layer and Fe₅₀Mn₅₀ (25 nm)/Ni_0.45Zn_0.55Fe₂O₄ (40 nm) bilayer films were prepared on Si(111) substrates by radio frequency magnetron sputtering at room temperature, and the influence of FeMn underlayer on the microstructure and magnetic property of Ni-Zn ferrite film has been investigated. It was found that the introduction of Fe₅₀Mn₅₀ underlayer resulted in a decrease from 7.1 to 3.1 kA/m in coercivity and increase from 0.22 to 0.60 in residual magnetization ratio of the ferrite film. The complex permeability μ = μ′ − iμ″ values of the films were measured at a frequency of up to 5 GHz. An obvious resonance peak at about 1.65 GHz of the bilayer film appeared in the permeability spectrum. The reason has been researched preliminarily and was ascribed to the change of the film's microstructure with FeMn underlayer.