Enhanced magnetization in Co and Ta-substituted BiFeO3 ceramics

Cobalt (Co) and tantalum (Ta) co-substituted BiFeO₃ polycrystalline ceramics were prepared by a solid-state reaction and their magnetic and dielectric properties were investigated. Magnetic hysteresis loops were clearly observed in co-substituted specimens and magnetization was greatly improved. The co-substitution decreased the electrical conductivity by six orders of magnitude along with the reduction of grain size. The magnetoelectric coupling was estimated in co-substituted BiFeO₃ by determining the changes of the dielectric constant with an external magnetic field.     

Growth and thermal stability of epitaxial BiFeO3 thin films

We have investigated the oxygen pressure and the temperature dependence on BiFeO₃ thin films deposited on SrTiO₃ substrates by pulsed laser deposition. Reflection high energy electron diffraction (RHEED), atomic force microscopy (AFM) and X-ray diffraction measurements indicate that high-quality epitaxial thin films are obtained for and T=650 °C. Outside of this pressure-temperature window, parasitic peaks attributed to β-Bi₂O₃ appear. We find an increase of the out-of-plane lattice parameter with oxygen pressure that we ascribe to Bi-deficiency due to its high volatility at low pressure. Ex-situ anneals have been performed and results show that as-grown single-phase BiFeO₃ thin films degrade after annealing, whereas as-grown BiFeO₃ containing impurity phases evolve toward a single-phase structure. These experiments demonstrate that parasitic phases can stabilize compounds which are usually unstable in air at elevated temperatures.     

Interface morphologies and magnetization characteristics of Co70Fe30 thin films deposited on conjugated polymer thin films

The surface and interface morphology and magnetization characteristics of Co₇₀Fe₃₀ thin films deposited on bare glass and p-Si/SiO₂ substrates and on conjugated polymer poly(3-hexylthiophene-2,5-diyl) (P3HT) thin films on such substrates have been studied by atomic force microscopy and magneto-optic Kerr effect. It was found that the average absolute magnitude of the coercive field of Co₇₀Fe₃₀ correlates with the roughness of the underlayer prior to Co₇₀Fe₃₀ deposition. P3HT deposited on p-Si/SiO₂ substrates possesses an increased surface roughness as compared to the p-Si/SiO₂ surface, but displays a decreased surface roughness as compared to the one of a bare glass substrate.     

L12 phase formation and giant exchange anisotropy in Mn3Ir/Co–Fe bilayers

The degree of order S of Mn–Ir layers and the exchange anisotropy of Mn–Ir/Co–Fe bilayers were investigated for various chemical compositions of Mn–Ir layers, underlayer materials, and underlayer thicknesses. It was found that: (1) The compositional range over which L1₂-phase Mn₃Ir could be formed is 22–32 at% Ir and giant exchange anisotropy is obtained in this range. (2) Ru is favorable as an underlayer material for avoiding interdiffusion with the Mn–Ir layer during deposition on the temperature elevated substrate. (3) The underlayer thickness could be reduced to 5 nm while maintaining a giant exchange anisotropy in excess of 1 erg/cm².     

Ferromagnetism of epitaxially grown CaRu1−xMxO3 (M=Ti, Mn) films

Epitaxial thin films of CaRu_1−xM_xO₃ (M=Ti, Mn) were fabricated on a (0 0 1)-SrTiO₃ substrate by spin-coat method using organometallic solutions (metal alkoxides). Results of X-ray diffraction and transmission electron microscopy indicate that the epitaxial films were grown pseudomorphically so as to align the [0 0 l] axis of the CaRu_1−xM_xO₃ films perpendicular to the (0 0 1) plane of the SrTiO₃ substrate. Ferromagnetism and metal-insulator transition are induced by the substitution of transition metal ions. The occurrence of ferromagnetism was explained qualitatively assuming a TiRu₆ cluster model for CaRu_1−xTi_xO₃ film and a mixed valence model for CaRu_1−xMn_xO₃ film. Ferromagnetism was also observed for layered CaRuO₃/CaMnO₃ film and CaRuO₃/CaMnO₃/CaRuO₃/CaMnO₃ multilayer film and the magnetism was explained by an interfacial exchange interaction model with magnetic Mn³⁺, Mn⁴⁺, and Ru⁵⁺ ions.     

Epitaxial growth and structural characterization of Pb(Fe1/2Nb1/2)O3 thin films

We have grown lead iron niobate thin films with composition Pb(Fe_1/2Nb_1/2)O₃ (PFN) on (0 0 1) SrTiO₃ substrates by pulsed laser deposition. The influence of the deposition conditions on the phase purity was studied. Due to similar thermodynamic stability spaces, a pyrochlore phase often coexists with the PFN perovskite phase. By optimizing the kinetic parameters, we succeeded in identifying a deposition window which resulted in epitaxial perovskite-phase PFN thin films with no identifiable trace of impurity phases appearing in the X-ray diffractograms. PFN films having thicknesses between 20 and 200 nm were smooth and epitaxially oriented with the substrate and as demonstrated by RHEED streaks which were aligned with the substrate axes. X-ray diffraction showed that the films were completely c-axis oriented and of excellent crystalline quality with low mosaicity (X-ray rocking curve FWHM?0.09°). The surface roughness of thin films was also investigated by atomic force microscopy. The root-mean-square roughness varies between 0.9 nm for 50-nm-thick films to 16 nm for 100-nm-thick films. We also observe a correlation between grain size, surface roughness and film thickness.     

How to obtain magnetocapacitance effects at room temperature: The case of Mn-doped BiFeO3

The magnetoelectric properties of a rhombohedrally distorted perovskite BiFe_0.7Mn_0.3O₃ are reported. An anomaly in the dielectric constant, related to enhanced thermal fluctuations around the antiferromagnetic transition, was induced near room temperature by the substitution of Mn for Fe in BiFeO₃. This substitution also brings about non-trivial magnetocapacitance effects at room temperature.     

Bi2O3 rods deposited under atmospheric pressure by means of halide CVD on c-sapphire

Bismuth Oxide (Bi₂O₃) rods are successfully prepared on δ-Bi₂O₃ films under atmospheric pressure by means of halide chemical vapour deposition using BiI₃ and O₂ as a starting material. The deposition of Bi₂O₃ rods strongly depends on the deposition temperature, the input partial pressure of BiI₃ and O₂ and the method for supplying O₂ gas. Bi₂O₃ rods can be obtained at [O₂]/[BiI₃] ratios of 500 and N₂:O₂=50:250. The length of the Bi₂O₃ rods increases proportionally from 2 to 30 μm, while their diameters of between 0.2 and 0.5 μm do not depend on the deposition time.     

New magnetic crystal,metastable metallic alloys Co1−xCux, prepared at strongly non-equilibrium conditions

Magnetic Co_1−xCu_x alloys in the form of single-crystal and polycrystalline films were grown under strongly non-equilibrium conditions using magnetron and triode sputtering techniques. It was found that these alloys could be obtained not only in the expected face-centered cubic structure, but also in a tetragonal phase, undetected earlier for present alloys. Results comparing some structural, magnetic and electric properties of these two phases are also presented here.     

Site-specific valence-band X-ray photoelectron spectra of a SrTiO3 single-crystal by X-ray standing wave technique

Site-specific valence-band X-ray photoelectron spectra of SrTiO₃ (111) were successfully obtained by using X-ray standing wave technique. Contributions of the Ti and SrO₃ derived states to the valence-band spectra were clearly separated. The spectra provided not only site-specific but also bulk-sensitive information on the SrTiO₃ crystal because of the use of a high-energy synchrotron X-ray source (hν=4750 eV) for photoelectron excitation with the large escape depth. The electronic structures calculated by the DV-Xα method using a (Sr₈Ti₂₇O₁₀₈)⁹²⁻ cluster model well reproduced the observed structures in the valence-band spectra. The partial density of states of both Ti and Sr ions in SrTiO₃ were mainly distributed over the bottom of the valence-band to produce the covalent bonding with O ions.     

Crystallization-dependent magnetic properties of Mn1.56Co0.96Ni0.48O4 thin films

The effects of magnetic property dependence of the Mn_1.56Co_0.96Ni_0.48O₄ (MCN) films on crystallization are investigated in the growth temperature of 450-750 °C. With the growth temperature increase, both the crystalline quality and the grain size improve. The MCN films exhibit paramagnetic to ferromagnetic transition and the paramagnetic parts fit to the modified Curie-Weiss law. The ferromagnetic couplings of the magnetic ions in the MCN films enhance at elevated growth temperature. The saturation magnetization at 5 K increases with increasing growth temperature, but coercive field decreases monotonously. The magnetic properties of the MCN films strongly depend on their microstructures.     

Angular dependence of tunneling magnetoresistance in La0.7Sr0.3MnO3 step-edge junctions

La_0.7Sr_0.3MnO₃ (LSMO) tunneling magnetoresistance (TMR) junctions have been fabricated on step-edge (0 0 1) SrTiO₃ substrates with a high step-edge angle. In the measurement of magnetoresistance (MR) ratio versus external magnetic field H, butterfly-like MR curves are clearly observed. The MR(H  ) curves vary with θ$\theta$, the angle between the applied magnetic field and the current direction in the substrate plane, showing anisotropic MR properties. A much broader MR(H) response is observed for the configuration of H perpendicular to the substrate plane. Additionally, the maxima-MR field H_p almost coincides with the coercive field H_c for θ<60°$\theta <60°$ but obeys a different form from _Hc(θ)$H_{\mathrm{c}}(\theta )$. The high-field junction resistance shows an intrinsic sin²θ${\sin }^2\theta$ angular dependence, while the low-field resistance shows an extrinsic cos(4θ)$\cos (4\theta )$ angular dependence. The distinctive features are mainly due to the induced magnetization anisotropy in the artificial steps of grain boundaries.     

AlF3 film deposited by IAD with end-Hall ion source using SF6 as working gas

A novel and effective process to fabricate high quality fluoride thin films was presented. Aluminum fluoride films deposited by a conventional thermal evaporation with an ion-assisted deposition (IAD) using SF₆ as a working gas at around room temperature were investigated. In this study, the optimal voltage and current, 50 V and 0.25 A, were found according to the optical properties of the films: high refractive index (1.489 at 193 nm), low optical absorption and extinction coefficient (<10⁻⁴ at 193 nm) in the UV range. The physical properties of the film are high packing density and amorphous without columnar structure. It was proved that using SF₆ working gas in IAD process is a good choice and significantly improves the quality of AlF₃ films.     

Domain structures in tetragonal Pb(Mg1/3Nb2/3)O3-PbTiO3 single crystals studied by piezoresponse force microscopy

The domain structures in (001) surface of Pb(Mg_1/3Nb_2/3)O₃-40% PbTiO₃ single crystals were investigated by piezoresponse force microscopy. Both micron-sized fingerprint 180° and parallel 90° domains were observed in the sample. Different sets of favourable {110} oriented domain patterns were found to meet, intersect or grow through each other. In addition, the piezoelectricity decreases sharply at the domain walls in 180° structures, but does not in the 90° domain structures.     

Multiferroic properties of Bi0.8La0.2FeO3/CoFe2O4 multilayer thin films

Bi_0.8La_0.2FeO₃/CoFe₂O₄ (BLFO/CFO) multilayer thin films (totally 20 layers BLFO and 19 layers CFO) were prepared on Pt/Ti/SiO₂/Si substrates by pulsed laser deposition. X-ray diffraction and transmission electron microscope measurements show that the films are polycrystalline and consisted of multilayered structure. Ferroelectric hysteresis loops with remnant polarization and saturated polarization of 4.2 and 13.3 μC/cm², respectively, were observed. On the other hand, the films show well-shaped magnetization hysteresis loops with saturated and remnant magnetization of 34.7 and 11.4 emu/cm³, respectively, which are significantly larger than pure BLFO thin films deposited under the same conditions. These results indicate that constructing epitaxial superlattice might be a promising way to fabricate multiferroics with improved properties.     

Magnetism in nanometer-thick TiOx/Co/TiOx/TiN/Si multilayered structures

Most studies on Co-doped TiO₂ system were focused on thin films grown by MBE-based methods. In this work we report the ferromagnetism of nanometer-thick-layered TiO₂/Co/TiO₂/TiN film grown on Si substrate by conventional magnetron sputtering. For the growth of TiO₂ on silicon, a non-oxide thermally stable material, TiN, was introduced to prevent Ti penetration into the Si substrate. Structural, magnetic, and transport measurements respectively by Raman, SQUID and Hall effect show that our samples are n-type semiconductors and exchange bias effect due to exchange coupling between Co and interfacial CoO. For the rapid vacuum annealed specimen, we found an enhanced loss and a Perminvar-type constricted hysteresis loop, which attributed to pinning of domain walls due to an induced anisotropy by the pair ordering in the metallic alloy of Co-Ti-Si.     

Fabrication and characterization of TS-1 films on α-Al2O3 substrates using TiCl3 as titanium source

The continuous and highly intergrown anatase-free TS-1 film was fabricated with TiCl₃ as the titanium source for the first time. The in situ nucleation and secondary growth method was employed to synthesize the TS-1 film. By means of scanning electron microscopy (SEM) images, X-ray diffraction (XRD) patterns, and FT-IR and UV-vis spectra measurements, the resulting film was observed to be anatase-free, continuous and highly intergrown with the MFI-type structure, and the Ti atoms existed only in tetrahedral coordination.     

Preparation and photocatalytic activity of CeO2/TiO2 interface composite film

The CeO₂/TiO₂ and TiO₂/CeO₂ interface composite films were prepared on glass substrates by the sol-gel process via dip-coating and calcining technique. The scanning electron microscopy (SEM) revealed that the TiO₂ layer has a compact and uniformity glasslike surface with 200 nm in thickness, and the CeO₂ layer has a coarse surface with 240 nm in thickness. The X-ray diffractometer (XRD) analysis showed that the TiO₂ layer is made up of anatase phase, and the CeO₂ layer is structured by cubic fluorite phase. Through a series of photo-degradation experiments, the relationship of the photocatalytic activity with the constituents of the films was studied. In virtue of the efficient interfacial charge separation via the process of electron transfer from TiO₂ to CeO₂, the photocatalytic activity of the CeO₂/TiO₂ composite film is high. Contrarily, the photocatalytic activity of the TiO₂/CeO₂ composite film is low, due to its inert surface made up of CeO₂ with broad bandwidth. Apart from the effect of the film structure, the effect of film thickness on photocatalytic activity was also discussed.     

Influence of mobile space charges on electrical properties of ferroelectric Bi3.5La0.5Ti3O12 thin films

Lanthanum-substituted bismuth titanate, Bi_3.5La_0.5Ti₃O₁₂ (i.e., x=0.5 in Bi_4−xLa_xTi₃O₁₂), thin films have been grown on Pt/Ti/SiO₂/Si substrates using pulsed laser deposition. The frequency dependence of the real part ε′(ω) and the imaginary part ε″(ω) of the dielectric constant has been studied. The ε′(ω) does not show any sudden change within the frequency range of 10²-10⁶ Hz. In contrast, the ε″(ω) shows a large dispersion as frequency decreases. The observed relaxation behavior in ε″(ω) can be explained in terms of a migration of oxygen vacancies in (Bi₂O₂)²⁺ layers, not in Bi₂Ti₃O₁₀ perovskite layers.     

Effect of Co layer thickness on the magnetic properties of Tb30Co70/SiNx/Co thin films

The SiN_x (20 nm)/Tb₃₀Co₇₀ (90 nm)/SiN_x (5 nm)/Co (3–37 nm)/SiN_x (10 nm)/Si multilayer films are deposited on naturally oxidized Si wafer by magnetron sputtering. The saturation magnetization (M_s) of the multilayer films is increased with the thickness of high M_s ferromagnetic Co layer. The perpendicular coercivity (_Hc⊥$H_{{\mathrm{c}}^{\perp }}$) value is increased with Co layer thickness as the thickness of the Co layer is lower than 15 nm and then decreases drastically when the thickness of the Co layer further increased. The increase of the _Hc⊥$H_{{\mathrm{c}}^{\perp }}$ value is owing to the interlayer exchange effect [Li Zhang, Physica B 390 (2007) 373] between TbCo and Co layers. Co under-layer with in-plane magnetic anisotropy would pin the magnetic moment of the TbCo layer near by the Co layer and cause the value of _Hc⊥$H_{{\mathrm{c}}^{\perp }}$ to increase. However, as the Co layer is thicker than a critical thickness, the _Hc⊥$H_{{\mathrm{c}}^{\perp }}$ value of the multilayer film would decrease. Therefore, the Co layer with in-plane magnetic anisotropy and soft magnetic properties is expected to dominate the magnetic properties of the multilayer films.