Enhanced magnetic properties of Nd–Fe–B thin films crystallized by heat treatment

Nd₂Fe₁₄B Φ phase crystallites were formed in Nd_16.7Fe_65.5B_17.8 thin films prepared by RF sputtering with subsequent heat treatment. The 2 μm-thick films were deposited onto 0.1 mm Mo sheets at an average substrate temperature (T_s) of 365°C. The enhanced magnetic properties of the magnetically anisotropic thin films were investigated using different heating rates (h_r) of 10°C, 20°C, 50°C and 100°C/min in an annealing experiment. Transformation from the amorphous phase to the crystalline phase is clearly manifested by the formation of fine crystallites embedded as a columnar matrix of Nd₂Fe₁₄B phase. High-resolution scanning electron microscope data of the cross-section of the annealed films show columnar stacking of Nd₂Fe₁₄B crystallites with sizes <500 nm. Transmission electron microscope observations revealed that the microstructure of these films having out-of-plane magnetization consists of uniformly distributed Φ phase with grain size around 400 nm together with small Nd rich particles. This grain size of Φ phase is comparable to the single domain particle diameter of Nd₂Fe₁₄B. Significant change in _iH_c, 4πM_r and 4πM_s with h_r was confirmed. Annealing conditions with a heating rate of 50°C/min to an annealing temperature (T_a) of 650°C for 30 min was consequently found to give optimum properties for the NdFeB thin films. The resulting magnetic properties, considered to be the effect of varying h_r were _iH_c= 1307–1357 kA/m, 4πM_r=0.78–1.06 T and 4πM_s=0.81–1.07 T.     

Effects of substitution of Ti for Fe in BiFeO3 films prepared by sol–gel process

Ti substituted BiFe_1−xTi_xO_3+δ films have been prepared on indium–tin oxide (ITO)/glass substrates by the sol–gel process. The films with x=0.00–0.20 were prepared at an annealing temperature of 600 °C. X-ray diffraction patterns indicate that all films adopt R3m structure and the films with x=0 and 0.10 show pure perovskite phase. Cross-section scanning shows the thickness of the films is about 300 nm. Through 0.05 Ti substitution, the 2P_r increases to 8.30 μC/cm² from 2.12 μC/cm² of the un-substituted BiFeO₃ film and show enhanced ferroelectricity at room temperature. The 2P_r values are 2.63 and 0.44 μC/cm² for the films with x=0.01 and 0.2, respectively. Moreover, the films with x=0.05 and 0.10 show enhanced dielectric property since the permittivity increases near 150 at the same measuring frequency. Through the substitution of Ti, the leakage conduction is reduced for the films with x=0.05–0.20.     

Magnetic anisotropic properties in Fe3O4 and CoFe2O4 ferrite epitaxy thin films

Epitaxial thin films of Fe₃O₄ and CoFe₂O₄ on MgO (0 0 1) substrates were grown by molecular beam epitaxy at low temperature growth process. Magnetization and hysteresis loop of both films were measured to investigate magnetic anisotropic properties at various temperatures. Anomalous magnetic properties are found to be correlated with crystalline, shape, and stress anisotropies. The Fe₃O₄ film below Verwey structural transition has a change in crystal structure, thus causing many anomalous magnetic properties. Crystalline anisotropy and anomalous magnetic properties are affected substantially by Co ions. The saturation magnetization of Co–ferrite film becomes much lower than that of Fe₃O₄ film, being very different from the bulks. It indicates that the low temperature growth process could not provide enough energy to have the lowest energy state.     

Effect of Co substitution on magnetic properties of Sr14Cu24O41

A series samples of Sr₁₄(Cu_1−xCo_x)₂₄O₄₁ (x=0, 0.02, 0.06, 0.14, 0.18) were prepared by standard solid-state reaction. X-ray diffraction measurements show that all the samples are single phase and their lattice parameter hardly changes by Co dopant. Electron diffraction experiments and X-ray photo-emission spectroscopy measurements reveal that Co ions substituted Cu ions in the chain. The measurements of magnetic susceptibility from 10 to 300 K in an applied magnetic field of 1.0 T show that Co dopant induces increase in susceptibility. The spin gaps are observed in all the samples, and decrease with increase in Co doping concentration. Fitting of the date indicates that strong antiferromagnetic interaction is induced and antiferromagnetic dimeried state may be formed due to Co³⁺ ions doping in these compounds.     

Improvement of the magnetic properties of low-neodymium magnets by minor addition of titanium

Rapidly solidified nanocomposite Nd₉Fe_77−xB₁₄Ti_x alloys, consisting of magnetic Nd₂Fe₁₄B phase and soft magnetic phases, were investigated. The effect of titanium addition on the structure and magnetic properties was studied. It was found that 2–4 at% Ti addition leads to substantial increase of the coercivity and maximum energy product, maintaining the remanence unchanged. The highest properties: J_r=0.81 T, _JH_c=907 kA/m, (BH)_max=99 kJ/m³, were achieved for the Nd₉Fe₇₃B₁₄Ti₄ alloy. This effect we attribute to the formation of fine and homogeneous grain structure and a change of the phase morphology in the Ti-containing alloys. The initial magnetization curve indicates a change of the coercivity mechanisms giving rise to pinning of domain walls, which is caused by reduction of the crystallite size.     

Magnetic properties in BaFe12O19 nanoparticles prepared under a magnetic field

It was observed that the nanocrystallites of BaFe₁₂O₁₉ formed at 140°C under a 0.25 T magnetic field exhibited a higher saturation magnetization (6.1 emu/g at room temperature) than that of the sample (1.1 emu/g) obtained under zero magnetic field. Both of the two approaches yielded plain-like particles with an average particle size of 12 nm. However, the Curie temperature (T_c), a direct measuring of the strength of superexchange interaction of Fe³⁺–O²⁻–Fe³⁺, increased from 410°C for the nanoparticles prepared without an external field applied to 452°C for the particles formed under a 0.25 T magnetic field, which indicates that external magnetic fields can improve the occupancy of magnetic ions and then increase the superexchange interaction. This was confirmed by electron paramagnetic resonance and Mössbauer spectrum analysis. The results present in this paper suggest that in addition to oxygen defects, surface non-magnetic layer and a fraction of finer particles in the superparamagnetic range, cation vacancies should be responsible for the decreasing of saturation magnetization in magnetic nanoparticles.     

Magnetic properties of Lu2Co17−xSix single crystals

The Co-sublattice anisotropy in Lu₂Co₁₇ consists of four competitive contributions from Co atoms at crystallographically different sites in the Th₂Ni₁₇-type of crystal structure, which result in the appearance of a spontaneous spin-reorientation transition (SRT) from the easy plane to the easy axis at elevated temperatures. In order to investigate this SRT in detail and to study the influence of Si substitution for Co on the magnetic anisotropy, magnetization measurements were performed on single crystals of Lu₂Co_17−xSi_x (x=0−3.4) grown by the Czochralski method. The SRT in Lu₂Co₁₇ was found to consist of two second-order spin reorientations, “easy-plane”–“easy-cone” at T_SR1≈680 K and “easy-cone”–“easy-axis” at T_SR2≈730 K. Upon Si substitution for Co, both SRTs shift toward the lower temperatures in Lu₂Co₁₆Si (T_SR1≈75 K and T_SR2≈130 K) with the further onset of the uniaxial type of magnetic anisotropy in the whole range of magnetic ordering for Lu₂Co_17−xSi_x compounds with x>1 due to a weakening of the easy-plane contribution from the Co atoms at the 6g and 12k sites to the total anisotropy.     

Composition and thermal-induced effects on the optical constants of Ge20Se80−xBix thin films

 The effects of composition and thermal annealing near crystallization temperature, T_c on the optical and structural properties of Ge₂₀Se_80−xBi_x (x=0, 2.5, 5 and 7.5 at%) was investigated. The influence of incorporation Bi content in Ge₂₀Se_80−xBi_x system results in a gradual decrease in the indirect optical gap from 1.89 to 1.44 eV, this behavior can be explained as increased tailing. On annealing, the optical band gap E_g decreases gradually for the crystallized films while the refractive index increases, this behavior can be attributed to transformation from amorphous to crystalline and was explained in the light of dangling bond model. The refractive index n of as-prepared and annealed films has been analyzed according to the Wwmple–DiDominico single oscillator model and the values of E_o and E_d were determined. The effect of annealing on the nature and degree of crystallization has been investigated by studying the structure using transmission electron microscope, X-ray diffraction and scanning electron microscope.     

Interacting Stoner–Wohlfarth behavior in hysteresis curves of Sm(CoFeCuZr)z magnets

Several magnets with different Zr contents were studied: Sm(Co_balFe_0.2Cu_0.1Zr_x)₈ (bal=balance; x=0, 0.02, 0.04, 0.06 and 0.08). The microstructure of the magnets includes three main phases, all crystallographically coherent: the cell phase Sm₂(Co,Fe)₁₇, the cell boundary phase Sm(Co,Cu)₅ and a lamellar Zr-rich phase, rhombohedral (ZrSm)₁Co₃. The hysteresis curves were compared with the Callen, Liu and Cullen (CLC) modification of the Stoner–Wohlfarth model for an isotropic distribution of interacting single-domain particles. Choosing reasonable values for the saturation magnetization M_s, the anisotropy field H_a, and the mean-field interactions of the CLC model, we were able to reproduce the main features of the hysteresis curves for the x=0.02 and 0.04 samples. For higher x values, X-ray diffraction Rietveld analysis revealed the presence of other “impurity” phases, among them cubic Zr₆(Co,Fe)₂₃, rhombohedral (SmZr)₅(CoFeCu)₁₉ and rhombohedral (SmZr)₂(CoFeCu)₇.     

Low-field negative magnetization and coercive-field magnetization reversal in transition metal chalcogenides; Cr2FeSe4 magnetic structure from neutron diffraction

Low-field negative magnetization, of the order of −10⁻¹ emu/g-Oe, from 4.2 K up to room temperature and higher (350 K), and coercive-field magnetization reversal are both present in Cr_(3−x)Fe_xX₄ for X=S, Se, Te and x=0 to 3, and for Cr₅Te₈ and Cr₇Te₈. For Cr₂FeSe₄ the zero-field-cooled (ZFC) magnetization is negative for 5 Oe and below. To obtain a more detailed knowledge of the magnetic phases involved in the observed magnetization versus temperature M(T) curves, we obtained and studied neutron diffraction (n.d.) scans on the compound Cr₂FeSe₄, taken at 14 temperatures from 4.2 to 300 K. For this same n.d. sample, the temperature for magnetization reversal of value −3×10⁻⁴ emu/g-Oe is 80 K in 40 Oe applied field, then the reversal disappears for 65 Oe applied field. The complex magnetic interactions responsible for this reversal are revealed in the hysteresis curves.     

Cuprite, paramelaconite and tenorite films deposited by reactive magnetron sputtering

Copper oxides films (Cu₂O, Cu₄O₃ and CuO) have been deposited by magnetron sputtering of a copper target in various Ar–O₂ reactive mixtures. The films are characterized by X-ray diffraction, scanning electron microscopy, four-point probe method and UV-Vis spectrometry. The three defined compounds in the Cu---O binary system can be deposited by varying the oxygen flow rate introduced into the reactor. All the films are crystallized with a mean crystal size ranging from 10 to about 35 nm. They are highly resistive and present a direct optical band gap higher than 2 eV. The application of a bias voltage during the deposition phase modifies the texture of the Cu₂O films and also induces a preferential resputtering of oxygen from the Cu₄O₃ ones. This resputtering phenomenon leads firstly to the occurrence of the cuprite phase mixed with the paramelaconite one and secondly to the amorphisation of the films. Finally, the thermal stability in air of cuprite, paramelaconite and tenorite films has been investigated. The results show that the stability of Cu₂O and Cu₄O₃ films in air is influenced by the thickness and/or the texture of the films. Tenorite films with a low optical band gap (1.71 eV) can be formed after air annealing at 350 °C of an unbiased cuprite film.     

Influence of silver doping on the photocatalytic activity of titania films

By means of X-ray diffraction, BET nitrogen adsorption, UV-Vis-NIR transmission spectroscopy, transmission electron microscope, scanning electron microscope, X-ray photoelectron spectroscopy and photodegradation of methylene blue, effects of Ag doping on the microstructure and photocatalytic activity of TiO₂ films prepared by sol–gel method were studied. It is found that with a suitable amount (2–4 mol%), the Ag dopant increases the photocatalytic activity of TiO₂ films. The mechanism can be attributed to that (1) anatase grain sizes decrease with Ag doping and the specific surface areas of doped TiO₂ films increase, the charge transfer in TiO₂ films is promoted; (2) by enhancing the electron–hole pairs separation and inhibiting their recombination, the Ag dopant enhances the charge pair separation efficiency for doped TiO₂ films.     

Valence and spin states in perovskites LaCo0.95M0.05O3 (M=Mg, Ga, Ti)

The samples LaCoO₃ with dilute substitutions on cobalt sites have been studied using the resistivity, thermopower and magnetic susceptibility measurements over the temperature range up to 900 K. The Co-site substitution does not affect the magnetic transition at 100 K and the onset of massive population of hole carriers at 500 K, characteristic for undoped LaCoO₃. On the other hand, the low-temperature transport and magnetism is markedly distinct for samples with extra charge on cobalt ions introduced by the heterovalent dopants (Mg²⁺, Ti⁴⁺) compared to samples with minor non-stoichiometry (LaCoO₃, Ga³⁺-doped sample). Magnetic properties suggest that these extra charges create thermally stable magnetic polarons of total S2–3. Common features of Co-site doped and La-site doped samples (La_1−xSr_xCoO₃) are discussed.     

Superconducting Nd1.85Ce0.15CuO4 films grown by the pulsed electron deposition technique

Nd_1.85Ce_0.15CuO_4−δ superconducting thin films were prepared on (1 0 0) SrTiO₃ substrates by pulsed electron deposition technique without reducing atmosphere. Oxygen content is finely controlled by high temperature vacuum annealing, and optimal superconductivity has been obtained. The deposition conditions of the film are discussed in details. Higher deposition temperature and lower gas pressure result in the loss of copper and the appearance of the foreign phase Ce_0.5Nd_0.5O_1.75. High quality Nd_1.85Ce_0.15CuO_4−δ epitaxial films are deposited at 840–870 °C in the mixed gas with a ratio of O₂:Ar = 1:3.     

Thickness dependence of microstructures in La0.9Sr0.1MnO3 thin films grown on exact-cut and miscut SrTiO3 substrates

The thickness dependence of microstructures of La_0.9Sr_0.1MnO₃ (LSMO) thin films grown on exact-cut and miscut SrTiO₃ (STO) substrates, respectively, was investigated by high-angle X-ray diffraction (HXRD), X-ray small-angle reflection (XSAR), X-ray reciprocal space mapping and atomic force microscopy (AFM). Results show that the LSMO films are in pseudocubic structure and are highly epitaxial [0 0 1]-oriented growth on the (0 0 1) STO substrates. The crystalline quality of the LSMO film is improved with thickness. The epitaxial relationship between the LSMO films and the STO substrates is [0 0 1]_LSMO[0 0 1]_EXACT-STO, and the LSMO films have a slight mosaic structure along the q_x direction for the samples grown on the exact-cut STO substrates. However, an oriented angle of about 0.24° exists between [0 0 1]_LSMO and [0 0 1]_MISCUT-STO, and the LSMO films have a mosaic structure along the q_z direction for that grown on the miscut STO substrates. The mosaic structure of both groups of the samples tends to reduce with thickness. The diffraction intensity of the (0 0 4) peaks increases with thickness of the LSMO film. The XSAR and AFM observations show that for both groups, the interface is sharp and the surface is rather smooth. The mechanism was discussed briefly.     

Magnetocaloric and magnetoresistance properties of La2/3Sr1/3Mn1−xCoxO3 compounds

Structural, magnetic, magnetoresistance and magnetocaloric studies on La_2/3Sr_1/3Mn_1−xCo_xO₃ compounds were reported. The samples were prepared by the conventional ceramic method. X-ray analysis showed the presence of one phase only, in all studied samples. From electrical resistance measurements it was found that the samples show large negative magnetoresistance behavior. The magnetic measurements were performed in a large temperature range, 4.2–750 K and external magnetic fields up to 5 T. The adiabatic magnetic entropy changes, |ΔS|, were determined from magnetization data. Large magnetocaloric effect (MCE) has been obtained in all studied samples.     

Deposition of MgO films by pulsed mid-frequency magnetron sputtering

MgO films were deposited by pulsed mid-frequency magnetron sputtering from metallic targets in the mixture of Ar and O₂ gas. The surface morphology, crystalline structure, and optical properties were characterized by using atomic force microscopy (AFM), X-ray diffraction (XRD), and spectroscopic ellipsometry, respectively. The secondary electron emission coefficients of MgO films were measured by using a self-made apparatus in He gas. A pronounced hysteresis phenomenon of target voltage, current, and deposition rate with increasing and decreasing O₂ flow rate was observed. The structure of films deposited at a metallic mode changes from Mg phase to the mixed Mg and MgO phase, and the films have a very rough surface. All the films deposited at oxide mode have high transparency and smooth surface, and show (2 2 0) preferred orientation growth. The refractive index and extinction coefficient at a wavelength of 670 nm for MgO films deposited at oxide mode with a O₂ flow rate of 3 sccm are 1.698 and 1.16×10⁻⁴, respectively. The secondary emission coefficient at a E/p of 57.8 V/(cm Torr) for MgO films deposited at a O₂ flow rate of 3 sccm is 0.16, which is higher than that of MgO films deposited by e-beam evaporation.     

Some insights in the sonochemical preparation of cobalt nano-particles

The preparation of cobalt nano-particles from a solution of Co(CO)₃(NO) in n-decane under ultrasonication with a frequency of 20 kHz yielded cobalt particles of a size of ca. 5 nm. The presence of either silica or oleic acid in the solution reduced the particle size to ca. 3 and 2 nm, respectively. The resulting particle size is independent of the ultrasonication time, initial Co(CO)₃(NO) concentration, ultrasound intensity and solution temperature. It is postulated that bubble collapse generates multiple nucleation sites resulting in the formation of cobalt particles with a rather uniform particle size distribution.     

Growth and characterization of model oxide catalysts

Oxide catalysts are frequently used to convert toxic species to environmentally benign molecules, and to prevent the formation of toxic species in the first place. In this paper, growth and characterization of model oxide systems employed in both approaches is discussed. An example of the former approach is the selective catalytic reduction (SCR) of NO emitted from power plants by NH₃, which employs tungsten and vanadium oxides supported on the anatase polymorph of TiO₂. To model SCR catalysts, epitaxial titanium, vanadium and tungsten oxide films were grown using molecular beam epitaxy and magnetron sputtering. Two different anatase orientations were grown on LaAlO₃ substrates and their interactions with vanadia were characterized. On LaAlO₃ (0 0 1), anatase exposed a (4 × 1) reconstructed (0 0 1) surface. Vanadia lifted the reconstruction and at 1 ML a (1 × 1) surface with mostly V⁵⁺ was observed. Continued V₂O₅ growth led to loss of order, but at high temperatures epitaxial VO₂ could be grown; vanadia behaved similarly on anatase films on LaAlO₃ (1 1 0). Results suggested that the monolayer is pseudomorphic with O adsorption oxidizing the surface V to 5+, since the anatase structure cannot accommodate more bulk oxygen, only a monolayer can be pseudomorphic and have only V⁵⁺. Thus the vanadia monolayer has unique structural and chemical properties that can help explain why vanadia monolayers on TiO₂ are much more active than bulk V₂O₅. For WO₃, a series of added row reconstructions were observed as the epitaxial films were reduced. The effect of these structures on surface chemistry was characterized by studying 1-propanol adsorption. The results indicated that the structure of the WO₃ surface did not alter its catalytic function but had a strong effect on reaction kinetics. As an example of a system where catalysts prevent the formation of toxic species, the reactivity of oxidized Pd surfaces used in CH₄ catalytic combustion were studied. An ordered PdO-like monolayer was found to be less reactive towards CO than adsorbed O on Pd. On the other hand, the PdO layer favored a lower activation energy C₃H₆ oxidation pathway. The results indicated that Pd oxidation reduces the sticking coefficient of reactive species but once molecules adsorb, the oxide surface can reduce the activation energy for subsequent reaction.     

氧气后处理对氧化锌薄膜紫外发射性质的影响

为了提高ZnO光发射效率和制备p型ZnO,对热处理的氧分压对薄膜的结构、形貌、光致光发射和ZnO/Si异质结的Ⅰ-Ⅴ特性的影响进行了研究.用直流反应溅射法在p型硅衬底上生长ZnO薄膜形成n-ZnO/P-Si异质结.在1000℃下用不同比例的氧和氨热处理,我们发现,在纯氮气中得到的样品有强的紫外发射(390nm),随氧气比例增大,紫外增强,同时绿光也产生并随之增强.但过大的氧分压反而产生多的受主缺陷,使越来越多的激发能量转移到发射能量低的绿光中心,从而使紫外减弱.在纯氧和无氧条件下热处理的俄歇谱表明纯氧下氧过量,而无氧下锌大大过量.ZnO/p-Si异质结的Ⅰ-Ⅴ特性表明,无氧热处理表现为典型的n-ZnO/p-Si异质结;而在纯氧气氛中处理后所得Ⅰ-Ⅴ曲线反向,这表明在高氧压下受主缺陷的产生,表明ZnO薄膜有可能由于高氧压热处理由n型转为p型.